CN1680028A - Solid super acidic catalyst for esterification and preparation method thereof - Google Patents
Solid super acidic catalyst for esterification and preparation method thereof Download PDFInfo
- Publication number
- CN1680028A CN1680028A CN 200510038295 CN200510038295A CN1680028A CN 1680028 A CN1680028 A CN 1680028A CN 200510038295 CN200510038295 CN 200510038295 CN 200510038295 A CN200510038295 A CN 200510038295A CN 1680028 A CN1680028 A CN 1680028A
- Authority
- CN
- China
- Prior art keywords
- preparation
- solid super
- acid catalyst
- super acid
- rare earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000007787 solid Substances 0.000 title claims abstract description 21
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 18
- 230000032050 esterification Effects 0.000 title claims description 16
- 230000002378 acidificating effect Effects 0.000 title 1
- 229910052761 rare earth metal Chemical class 0.000 claims abstract description 16
- 239000003930 superacid Substances 0.000 claims abstract description 16
- 238000010992 reflux Methods 0.000 claims abstract description 15
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 8
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 34
- 239000010936 titanium Substances 0.000 claims description 20
- 238000007598 dipping method Methods 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 241000907661 Pieris rapae Species 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000002075 main ingredient Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- -1 rare earth ion Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 10
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 abstract description 5
- 150000002910 rare earth metals Chemical class 0.000 abstract description 5
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical class [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical class [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229910000348 titanium sulfate Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 238000006555 catalytic reaction Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000004032 superbase Substances 0.000 description 1
- 150000007525 superbases Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a catalyst for synthesizing tetraisooctyl pyromellitate (TOPM for short) and a preparation method thereof. SO is prepared from titanium sulfate, aluminum nitrate, sulfuric acid and rare earth salt4 2－Novel solid superacid of/Ti-Al-M-O, M being one of the rare earth elements (Re, Tm, La); in a reflux reaction device with pyromellitic acid diAnhydride and isooctyl alcohol are used as raw materials, and the solid superacid is used as a catalyst to catalyze and synthesize tetraisooctyl pyromellitate (TOPM for short). The yield and the selectivity of the TOPM respectively reach more than 99 percent and 99 percent. The catalyst of the invention has the advantages of convenient preparation, high activity, good selectivity, long service life, low reaction temperature, light color of esterification reaction products and good industrialization prospect.
Description
Technical field
The present invention relates to a kind of solid superstrong acid catalyst of esterification and preparation method thereof, relate in particular to rare earth modified solid superstrong acid catalyst of esterification of a kind of usefulness and preparation method thereof.
Background technology
Carboxylicesters is a kind of important organic compound, and it not only can be used as the raw material of organic synthesis, and is important fine chemical product, is widely used in industries such as spices, daily use chemicals, food, medicine, rubber, coating.Along with the develop rapidly of science and technology and the raising of people's living standard, people are also increasing to its demand.The traditional synthetic method of this product is to be raw material with corresponding carboxylic acid and alcohol, adopting the vitriol oil is that catalyzer is produced, although cheap, the active high advantage that with the vitriol oil is that catalyzer has, but this method is unsatisfactory, some deficiency below main the existence: 1. the oxidisability of the vitriol oil and dewatering cause a series of side reaction, as esterification, carbonization etc., make and contain sulfuric ester, ether, unsaturated compound etc. in the by product, for the recovery of the refining and raw material of product often brings difficulty, product yield is lower simultaneously.2. the vitriol oil has intensive corrodibility etching apparatus.3. the discharging of a large amount of spent acid, cause atmospheric pollution [Wei Rongbao etc. Liaoning chemical industry .95.3:28-29].Therefore change the catalyzer of esterification, seek the focus that corresponding new esterifying reaction method becomes current research and development.
The synthetic for the first time SO of Hino in 1979 and Arata
4 2-/ ZrO
2Solid super-strong acid [M.Hino, K.Arata, J.Am.Chem.Soc., 101 (21), 6439 (1979)], its strength of acid can reach 100%H
2SO
410,000 times.Solid super-strong acid has its distinctive advantage, etching reactor not, be easy to separate with reactant, to some reaction preference height, can use repeatedly, high temperature resistant, easy to prepare [field portion great three. super acids and super base. Cui Shengfan translates. Beijing Chemical Industry Press], so this class catalyzer more and more is subjected to people's favor, the application in esterification is more and more widely.
Chen Li etc. [in old, Ding Laixin, Cui Liyan. Institutes Of Technology Of Nanjing's journal, 1996,20 (6): 501～504] use SO
4 2-/ TiO
2-La
2O
3Synthetic TOPM, transformation efficiency was more than 98% for pyromellitic acid anhydride (being called for short equal acid anhydride) when catalyst levels was 8.9% (with respect to the mass percent of pyromellitic acid anhydride), and catalyst levels is big, and cost is higher, reuses 5 rear catalysts inactivation.We are once with SO
4 2-/ TiO
2-Al
2O
3Be applied to the synthetic of Pyromellitic Acid four different monooctyl esters and be applied patent [application number: 200410064694.1], optimum preparating condition is: the atomic ratio of Ti and Al is 1: 0.3, and sulfuric acid concentration is 0.5mol1
-1, maturing temperature is 673K.Just can reach about 99.4% though transformation efficiency is the highest behind reaction 2h under the catalyzer optimum preparating condition, reaction 3h can reach 99.6%, but reaction 2h transformation efficiency all is lower than 98.5% under other preparation conditions, illustrate that preparation condition is very big to the reactive behavior influence, preparation condition has deviation a little, the catalytic activity of catalyzer is just not high, and preparation condition is very harsh.
Summary of the invention
The objective of the invention is big, the deficiencies such as cost is high, preparation condition harshness of consumption at existing catalyst for esterification reaction, provide a kind of free from environmental pollution, easy to prepare, catalytic activity height, the solid super acid catalyst system SO that selectivity is good, the life-span is long, product color is good
4 2-/ Ti-Al-M-O, M are a kind of of rare earth element (Re, Tm, La), and to replace this traditional catalyzer of sulfuric acid, another object of the present invention provides this Preparation of catalysts method.
Technical scheme of the present invention is: catalyzer provided by the invention is a kind of solid super acid catalyst that is used for esterification, its main ingredient the has been load SO of rare earth element
4 2-/ Ti-Al-M-O, wherein M is a kind of among rare earth element Re, Tm or the La.Catalyst active carrier is M-TiO
2-Al
2O
3Complex metal oxides, M are a kind of of Re, Tm or La, and the main active component of catalyzer is SO
4 2-, TiO
2, Al
2O
3, rare earth oxide, SO
4 2-By combining with metal oxide behind dipping, the high-temperature activation; The molar content of titanium, aluminium, rare earth element M is respectively in the catalyzer: mol (Al) % is 10～49%, and mol (Ti) % is 48～87%, mol (M) % is 1～5%.
The present invention also provides this preparation method who is used for the esterification solid super acid catalyst, and its preparation process comprises, at first prepares the TiO of certain Ti, Al atomic ratio with coprecipitation method
2-Al
2O
3Mixed powder; Under reflux state, flood a kind of nitrate solution of certain density rare earth element then; After filtration after the drying, at certain density H
2SO
4Flood in the solution; After roasting makes the catalyzer finished product.Concrete steps are as described below:
A. to contain Ti and Al mol ratio be 1: 0.3～1: 1 Ti (SO in preparation
4)
2And Al (NO
3)
39H
2O mixing salt solution a;
B. use NH
3H
2PH value to 6～10 of O adjusting mixing salt solution a obtain containing the mixture of white precipitate; After ageing after 6～24 hours, suction filtration, washing, oven dry grinds then to≤200 orders, obtains white powder c;
C. white powder c is joined and contain rare earth ion Re, Tm or La concentration is 0.1～0.3molL
-1Nitrate solution in, under reflux state, about dipping 1h, filter, oven dry obtains white powder d;
D. use 0.1～1molL
-1H
2SO
4Solution and white powder d are by 10～30mlg
-1Ratio stirs dipping down, and suction filtration is gone out unnecessary H then
2SO
4, drying grinds then to≤200 orders, obtains white powder e; In air atmosphere, obtain solid super acid catalyst after 523～973K roasting temperature white powder e activation.Wherein use NH
3H
2O regulates Ti (SO
4)
2And Al (NO
3)
39H
2The pH value of O mixing salt solution is preferably 7～9.The temperature of roasting is preferably 673K～923K in air atmosphere.H
2SO
4Impregnation concentration is preferably 0.3～1molL
-1
The synthetic TOPM of the catalysis of catalyzer is active to be investigated as following: take by weighing 0.1g (account for equal acid anhydride 1.8%) catalyzer, take by weighing the 5.5g pyromellitic acid anhydride, measure the 27ml isooctyl alcohol and join in the there-necked flask.Plug thermometer, reflux condensing tube, water separator on the there-necked flask, pick up counting when beginning to reflux, after reaction for some time, leach catalyzer, excessive isooctyl alcohol is isolated in underpressure distillation, obtains thick ester product.The analytical procedure of being narrated in the mensuration according to GB GB/T1668-95 softening agent acid number and acidity is carried out the acid number analysis to product, and calculates equal acid anhydride transformation efficiency.Catalyzer provided by the invention is as the solid super acid catalyst of the synthetic TOPM of catalysis, and behind reaction 2h under 165～185 ℃, the reaction yield can reach more than 99%.Have very high activity and selectivity, and the product transparent color and luster; Method for preparing catalyst is simple, and cost is lower, and the life-span is longer.
Beneficial effect
1, catalyst levels is little, and catalytic activity is improved, and life of catalyst has obtained prolongation.When consumption is 1.8% (accounting for the consumption of equal acid anhydride), and all the acid anhydride transformation efficiency is the highest behind reaction 2h under the catalyzer optimum preparating condition just can reach about 99.9%, the reaction after-filtration goes out catalyzer and directly applies to down secondary response without any processing, repeated use is reacted yield and still can be reached more than 98% more than 19 times, and the product color that obtains is yellowish, the quality product height.As seen pass through rare earth modified after, the catalytic activity of catalyzer is improved, life of catalyst has obtained prolongation.
2, the Preparation of Catalyst condition is convenient, and preparation condition is more prone to control.Through after rare earth modified, at the preparation condition scope (maturing temperature 623～873K of broad; Sulfuric acid concentration 0.1～0.7mol1
-1) internal reaction 2h yield can reach more than 99%; In the patent [application number: 200410064694.1], optimum preparating condition is: the atomic ratio of Ti and Al is 1: 0.3, and sulfuric acid concentration is 0.5mol1
-1, maturing temperature is 673K.Just can reach about 99.4% though transformation efficiency is the highest behind reaction 2h under the catalyzer optimum preparating condition, but reaction 2h transformation efficiency all is lower than 98.5% under other preparation conditions, illustrate that preparation condition is very big to the reactive behavior influence, preparation condition has deviation a little, the catalytic activity of catalyzer is just not high, and preparation condition is very harsh.As seen, through after rare earth modified, the Preparation of Catalyst condition is convenient, and preparation condition is more prone to control.
Embodiment
Below by embodiment effect of the present invention is described further.
Embodiment one:
Preparation of catalysts
Two kinds of salts solutions stirrings that at room temperature with Ti, Al atomic ratio are 1: 0.3 (molar content of Al is 23%) are evenly mixed, use NH
3H
2The pH value of O regulator solution is 10, and ageing 8h after suction filtration, the washing, with the down dry 15～24h of 383～413K, grinds to≤200 orders.Use 0.1molL then
-1Tm (NO
3)
3Solution is according to 15mlg
-1Ratio reflux state dipping 2h, use 0.5molL
-1H
2SO
4Solution is according to 10mlg
-1Ratio dipping 20min, with dry 3h under the 393K,, in air atmosphere, be placed in the moisture eliminator and preserve in 653K roasting temperature 5h.
TOPM is synthesized in catalysis
Take by weighing the catalyzer of 0.1g (account for equal acid anhydride weight 1.8%), take by weighing the 5.5g pyromellitic dianhydride, measure the 27ml isooctyl alcohol and join in the there-necked flask.Plug thermometer, reflux condensing tube, water separator on the there-necked flask, pick up counting when beginning to reflux, temperature of reaction is 168～184 ℃, behind the reaction 2h, leaches catalyzer, and excessive isooctyl alcohol is isolated in underpressure distillation, obtains thick ester product.The analytical procedure of being narrated in the mensuration according to GB GB/T 1668-95 softening agent acid number and acidity is carried out the acid number analysis to product, and calculate the reaction yield be 99.5%.
Embodiment two:
Preparation of catalysts
Two kinds of salts solutions stirrings that at room temperature with Ti, Al atomic ratio are 1: 0.7 (molar content of Al is 41.2%) are evenly mixed, use NH
3H
2The pH value of O regulator solution is 6, and ageing 8h after suction filtration, the washing, with dry 24h under 383～393K, grinds to≤200 orders, uses 0.2molL then
-1Tm (NO
3)
3Solution is according to 15mlg
-1Ratio reflux state dipping 50min after, use 0.5molL
-1H
2SO
4Solution is according to 10mlg
-1Ratio dipping 20min, with dry 2h under the 393K, grind to≤200 orders, in air atmosphere, be placed in the moisture eliminator and preserve in 773K roasting temperature 5h.
TOPM is synthesized in catalysis
Esterification is carried out according to the method for example 1, and temperature of reaction is 169～185 ℃, and the reaction yield is 99.3%.
Embodiment three
Two kinds of salts solutions stirrings that at room temperature with Ti, Al atomic ratio are 1: 1 (molar content of Al is 50%) are evenly mixed, use NH
3H
2The pH value of O regulator solution is 8, and ageing 6h after suction filtration, the washing, with dry 24h under the 383K, grinds to≤200 orders, uses 0.2molL then
-1La (NO
3)
3Solution is according to 15mlg
-1Ratio reflux state dipping 20min after, with the H of 0.1molL
2SO
4Solution, grinds to≤200 orders with dry 1h under the 393K according to the ratio of 10mlg dipping 25min, is placed in the moisture eliminator in 873K roasting temperature 5h in air atmosphere and preserves.
TOPM is synthesized in catalysis
Esterification is carried out according to the method for example 1, and temperature of reaction is 165～189 ℃, and the reaction yield is 98.0%
Embodiment four
Preparation of catalysts
Two kinds of salts solutions stirrings that at room temperature with Ti, Al atomic ratio are 1: 0.3 (molar content of Al is 23.1%) are evenly mixed, use NH
3H
2The pH value of O regulator solution is 7, and ageing 8h after suction filtration, the washing, with dry 24h under the 383K, grinds to≤200 orders, uses 0.3molL then
-1La (NO
3)
3Solution is according to 15mlg
-1Ratio reflux state dipping 1h after, use 0.4molL
-1H
2SO
4Solution is according to 10mlg
-1Ratio dipping 30min, with dry 3h under the 393K, grind to≤200 orders, in air atmosphere, be placed in the moisture eliminator and preserve in 623K roasting temperature 5h.
TOPM is synthesized in catalysis
Esterification is carried out according to the method for example 1, and temperature of reaction is 160～183 ℃, and the reaction yield is 99.9%.
Embodiment five
Preparation of catalysts
Two kinds of salts solutions stirrings that at room temperature with Ti, Al atomic ratio are 1: 0.5 (molar content of Al is 33.3%) are evenly mixed, use NH
3H
2The pH value of O regulator solution is 9, and ageing 24h after suction filtration, the washing, with dry 24h under the 383K, grinds to≤200 orders, uses 0.2molL then
-1Re (NO
3)
3Solution is according to 15mlg
-1Ratio reflux state dipping 1h after, use 0.7molL
-1H
2SO
4Solution is according to 10mlg
-1Ratio dipping 30min, with dry 50min under the 393K, grind to≤200 orders, in air atmosphere, be placed in the moisture eliminator and preserve in 623K roasting temperature 5h.
TOPM is synthesized in catalysis
Esterification is carried out according to the method for example 1, and temperature of reaction is 164～188 ℃, and the reaction yield is 99.6%.
Embodiment six
Preparation of catalysts
Two kinds of salts solutions stirrings that at room temperature with Ti, Al atomic ratio are 1: 0.3 (molar content of Al is 23.1%) are evenly mixed, use NH
3H
2The pH value of O regulator solution is 8, and ageing 24h after suction filtration, the washing, with dry 24h under the 383K, grinds to≤200 orders, uses 0.2molL then
-1Re (NO
3)
3Solution is according to 15mlg
-1Ratio reflux state dipping 40min after, use 0.5molL
-1H
2SO
4Solution is according to 30mlg
-1Ratio dipping 5min, with dry 2h under the 393K, grind to≤200 orders, in air atmosphere, be placed in the moisture eliminator and preserve in 623K roasting temperature 5h.
TOPM is synthesized in catalysis
Esterification is carried out according to the method for example 1, and temperature of reaction is 160～181 ℃, and the reaction yield is 99.5%.
Embodiment seven
Preparation of catalysts
Two kinds of salts solutions stirrings that at room temperature with Ti, Al atomic ratio are 1: 0.5 (molar content of Al is 23.1%) are evenly mixed, use NH
3H
2The pH value of O regulator solution is 9, and ageing 24h after suction filtration, the washing, with dry 24h under the 383K, grinds to≤200 orders, uses 0.2molL then
-1La (NO
3)
3Solution is according to 15mlg
-1Ratio reflux state dipping 30min after, use 0.6molL
-1H
2SO
4Solution is according to 15mlg
-1Ratio dipping 15min, with dry 2h under the 393K, grind to≤200 orders, in air atmosphere, be placed in the moisture eliminator and preserve in 623K roasting temperature 5h.
TOPM is synthesized in catalysis
Esterification is carried out according to the method for example 1, and temperature of reaction is 160～181 ℃, and the reaction yield is 99.3%.
Claims (7)
1, a kind of solid super acid catalyst that is used for esterification, the main ingredient that it is characterized in that solid super acid catalyst the has been load SO of rare earth element
4 2-/ Ti-Al-M-O, wherein M is a kind of among rare earth element Re, Tm or the La.
2, according to solid super acid catalyst described in the claim 1, the active carrier that it is characterized in that is M-TiO
2-Al
2O
3Complex metal oxides, M are a kind of of Re, Tm or La.
3, according to solid super acid catalyst described in claims 1, it is characterized in that the molar content of titanium in the catalyzer, aluminium, rare earth element M is respectively: mol (Al) % is 10～49%, and mol (Ti) % is 48～87%, mol (M) % is 1～5%.
4, the described Preparation of catalysts method of claim 1, its concrete steps are as described below:
A. to contain Ti and Al mol ratio be 1: 0.3～1: 1 Ti (SO in preparation
4)
2And Al (NO
3)
39H
2O mixing salt solution a;
B. use NH
3H
2PH value to 6～10 of O adjusting mixing salt solution a obtain containing the mixture of white precipitate; After ageing after 6～24 hours, suction filtration, washing, oven dry grinds then to≤200 orders, obtains white powder c;
C. white powder c is joined and contain rare earth ion Re, Tm or La concentration is 0.1～0.3molL
-1Nitrate solution in, under reflux state, flood, filter, oven dry obtains white powder d;
D. use 0.1～1molL
-1H
2SO
4Solution and white powder d are by 10～30mlg
-1Ratio stirs dipping down, and suction filtration is gone out unnecessary H then
2SO
4, drying grinds then to≤200 orders, obtains white powder e; In air atmosphere, obtain solid super acid catalyst after 523～973K roasting temperature white powder e activation.
5,, it is characterized in that using NH according to the preparation method of the described solid super acid catalyst of claim 4
3H
2O regulates Ti (SO
4)
2And Al (NO
3)
39H
2The pH value of O mixing salt solution is 7～9.
6, according to the preparation method of the described solid super acid catalyst of claim 4, the temperature that it is characterized in that roasting in the air atmosphere is 673K～923K.
7, according to the preparation method of solid super acid catalyst described in the claim 4, it is characterized in that H
2SO
4Impregnation concentration is 0.3～1molL
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100382952A CN1327956C (en) | 2005-01-31 | 2005-01-31 | Preparation method of solid super acidic catalyst for preparing tetraisooctyl pyromellitate by reaction of pyromellitic acid and isooctyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100382952A CN1327956C (en) | 2005-01-31 | 2005-01-31 | Preparation method of solid super acidic catalyst for preparing tetraisooctyl pyromellitate by reaction of pyromellitic acid and isooctyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1680028A true CN1680028A (en) | 2005-10-12 |
| CN1327956C CN1327956C (en) | 2007-07-25 |
Family
ID=35067003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100382952A Expired - Fee Related CN1327956C (en) | 2005-01-31 | 2005-01-31 | Preparation method of solid super acidic catalyst for preparing tetraisooctyl pyromellitate by reaction of pyromellitic acid and isooctyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1327956C (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851333A (en) * | 2010-05-28 | 2010-10-06 | 杭州师范大学 | Method for preparing methyl phenyl hydrogen-containing silicone oil by rare earth super acid catalysis |
| CN102294252A (en) * | 2011-07-18 | 2011-12-28 | 李搏 | Production method of solid super acidic catalyst S04<2->/Sb-SnO2 |
| CN105175258A (en) * | 2015-10-23 | 2015-12-23 | 南京科技职业学院 | Synthesis method of C10 mixed ester plasticizer |
| CN105562038A (en) * | 2015-12-25 | 2016-05-11 | 江西西林科股份有限公司 | Preparation method of solid superacid catalyst used for esterification of acid type anti-wear agent and method for catalysis preparation of fatty acid ester anti-wear agent by solid superacid catalyst |
| CN106622302A (en) * | 2016-11-29 | 2017-05-10 | 华东理工大学 | Preparation method of catalyst for preparation of high-purity olefin |
| CN109126832A (en) * | 2018-08-07 | 2019-01-04 | 陈子清 | A kind of synthetic method of solid super-strong acid |
| CN109499586A (en) * | 2018-12-05 | 2019-03-22 | 怀化学院 | Rare earth modified solid super acid catalyst and preparation method thereof |
| CN111909037A (en) * | 2020-09-01 | 2020-11-10 | 潍坊弘润新材料有限公司 | Continuous production method of tetraisooctyl pyromellitate |
| CN113929572A (en) * | 2021-11-11 | 2022-01-14 | 润泰新材料股份有限公司 | Method for synthesizing triethylene glycol dipropyl ester and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108906083A (en) * | 2018-07-30 | 2018-11-30 | 陈蓉 | A method of precipitating infusion process prepares iron oxide load sulfate ion type solid super-strong acid |
| CN108927180A (en) * | 2018-07-30 | 2018-12-04 | 李云军 | A kind of preparation method of nanometer ferro oxide load sulfate ion type solid super-strong acid |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5212136A (en) * | 1991-11-27 | 1993-05-18 | Sun Company, Inc (R&M) | Solid-acid alkylation catalyst compositions for alkylation processes |
| JPH0769955A (en) * | 1993-08-27 | 1995-03-14 | Inoue Koryo Seizosho:Kk | Production of acetal |
| CN1088404C (en) * | 1998-12-15 | 2002-07-31 | 南京师范大学 | Molecular sieve catalyst for synthesis of dibutyl phthalate and its preparing process |
| CN1142017C (en) * | 2001-11-29 | 2004-03-17 | 中国石油化工股份有限公司 | Prepn process of solid super acidic catalyst |
| CN1243712C (en) * | 2003-08-07 | 2006-03-01 | 南京林业大学 | Synthesis method of propylene glycol methyl ether propionate |
-
2005
- 2005-01-31 CN CNB2005100382952A patent/CN1327956C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851333A (en) * | 2010-05-28 | 2010-10-06 | 杭州师范大学 | Method for preparing methyl phenyl hydrogen-containing silicone oil by rare earth super acid catalysis |
| CN102294252A (en) * | 2011-07-18 | 2011-12-28 | 李搏 | Production method of solid super acidic catalyst S04<2->/Sb-SnO2 |
| CN102294252B (en) * | 2011-07-18 | 2013-03-20 | 李搏 | Production method of solid super acidic catalyst S04<2->/Sb-SnO2 |
| CN105175258A (en) * | 2015-10-23 | 2015-12-23 | 南京科技职业学院 | Synthesis method of C10 mixed ester plasticizer |
| CN105562038B (en) * | 2015-12-25 | 2017-12-29 | 江西西林科股份有限公司 | A kind of method that solid super acid catalyst for the esterification of acid type antiwear additive prepares fatty acid ester antiwear additive |
| CN105562038A (en) * | 2015-12-25 | 2016-05-11 | 江西西林科股份有限公司 | Preparation method of solid superacid catalyst used for esterification of acid type anti-wear agent and method for catalysis preparation of fatty acid ester anti-wear agent by solid superacid catalyst |
| CN106622302A (en) * | 2016-11-29 | 2017-05-10 | 华东理工大学 | Preparation method of catalyst for preparation of high-purity olefin |
| CN109126832A (en) * | 2018-08-07 | 2019-01-04 | 陈子清 | A kind of synthetic method of solid super-strong acid |
| CN109126832B (en) * | 2018-08-07 | 2021-10-26 | 陈子清 | Method for synthesizing solid super acid |
| CN109499586A (en) * | 2018-12-05 | 2019-03-22 | 怀化学院 | Rare earth modified solid super acid catalyst and preparation method thereof |
| CN111909037A (en) * | 2020-09-01 | 2020-11-10 | 潍坊弘润新材料有限公司 | Continuous production method of tetraisooctyl pyromellitate |
| CN111909037B (en) * | 2020-09-01 | 2023-04-18 | 潍坊弘润新材料有限公司 | Continuous production method of tetraisooctyl pyromellitate |
| CN113929572A (en) * | 2021-11-11 | 2022-01-14 | 润泰新材料股份有限公司 | Method for synthesizing triethylene glycol dipropyl ester and application thereof |
| CN113929572B (en) * | 2021-11-11 | 2024-03-15 | 润泰新材料股份有限公司 | Method for synthesizing triethylene glycol dipropyl ester and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1327956C (en) | 2007-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1680028A (en) | Solid super acidic catalyst for esterification and preparation method thereof | |
| CN101347740B (en) | Method for preparing SO4<2->/ZrO2-MxOy solid superacid catalyst and use | |
| CN109482241B (en) | TiO2/MOF-5 photocatalyst and preparation method thereof | |
| CN1189242C (en) | Granular solid super strong acid catalyst and its preparing method | |
| CN110327976B (en) | Photocatalyst and preparation method and application thereof | |
| WO2011108195A1 (en) | Method for producing hydrotalcite-like compound, hydrotalcite-like compound, complex oxide, anion adsorbent, and solid base catalyst | |
| CN109499619A (en) | TiO2/ MIL-101 photochemical catalyst and preparation method thereof | |
| CN111054425B (en) | hydrotalcite/MCM-41 mesoporous silicon composite solid base catalyst and in-situ preparation method and application thereof | |
| CN109482242A (en) | Ni adulterates TiO2/ MOF-5 photochemical catalyst and preparation method thereof | |
| CN101318139A (en) | Composite solid super acidic catalyst and preparation method thereof | |
| CN101829559A (en) | Preparation method and application of WO3/ZrO2 solid super acidic catalyst | |
| CN109607561A (en) | Laminar hetero-atom molecular-sieve and its synthetic method | |
| CN100411735C (en) | Solid super acidic catalyst and its preparing method | |
| CN1157256C (en) | Solid acid with high selectivity and activity for esterification and its prpen. | |
| CN1301155C (en) | Preparation and application of solid acid catalyst for synthesizing tetraisooctyl pyromellitate | |
| CN1739853A (en) | Composite oxide solid acid catalyst and its prepn process | |
| CN1935373A (en) | Rare-earth-containing composite solid super acidic catalyst and its preparing method | |
| JP3985116B2 (en) | Zirconium hydroxide and method for producing the same | |
| CN1565724A (en) | Cerium-titanium solid solution and its preparing method | |
| CN114634206B (en) | Preparation method of manganous-manganic oxide | |
| CN110143871B (en) | Preparation method of dicarboxylic acid diol ester | |
| CN1073885C (en) | Solid super-strong acid and its prepn. | |
| CN111153801A (en) | Preparation method of aromatic carboxylic ester compound | |
| CN118080019B (en) | Phytic acid-aluminum catalyst for preparing asymmetric organic carbonic ester | |
| CN1636873A (en) | Mesoporous Zr-Si molecular sieve and its synthesis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Nanjing Well Chemical Co.,Ltd. Assignor: Nanjing Tech University Contract fulfillment period: 2006.12.6 to 2015.1.30 Contract record no.: 2008320001084 Denomination of invention: Solid superstrong acid catalyst of esterification of preparation thereof Granted publication date: 20070725 License type: Exclusive license Record date: 20081103 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2006.12.6 TO 2015.1.30; CHANGE OF CONTRACT Name of requester: NANJING WEIER CHEMICAL ENGINEERING CO., LTD. Effective date: 20081103 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070725 Termination date: 20150131 |
|
| EXPY | Termination of patent right or utility model |