CN110201716A - A kind of group modified order mesoporous C/SiO of hydramine2Carried heteropoly acid catalyst and its preparation method and application - Google Patents
A kind of group modified order mesoporous C/SiO of hydramine2Carried heteropoly acid catalyst and its preparation method and application Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The present invention relates to a kind of group modified mesoporous C/SiO of hydramine2The application of the preparation method and its catalyzed alkene of carried heteropoly acid catalyst and carboxylic acid addition esterification.The group modified mesoporous C/SiO of the hydramine2The preparation method of carried heteropoly acid catalyst, organic formwork agent and hydramine substance are dissolved in acid condition first, heteropoly acid aqueous solution is slowly added dropwise after hydrolyzing silicon source in addition silicon source stirring, rear hydrothermal crystallizing is sufficiently stirred for a period of time, the method for solution filtration washing dry roasting after crystallization is made.The group modified order mesoporous C/SiO of hydramine of the present invention2Carried heteropoly acid catalyst preparation process is simple, and acid and acid amount is adjustable, and aperture is uniform controllable.It can be few in catalyst amount, under higher temperature, condition of no solvent, efficiently and stably catalyzed alkene and carboxylic acid high conversion, high selectivity carboxylate, improve the atom utilization of the atomic economy reaction, the energy consumption of separation product can be effectively reduced, equipment investment is reduced.
Description
Technical field
The invention belongs to technical field of chemical synthesis, are related to a kind of group modified order mesoporous C/SiO of hydramine2It loads miscellaneous
The preparation of polyacid catalyst and it is applied to carboxylic acid and alkene addition reaction and produces carboxylate.
Background technique
Carboxylic acid ester compound has good dissolubility, living on coating, daily chemical product, ink, industrial cleaning agent, surface
Property the fields such as agent there is extensive use.The atomic economy reaction that carboxylate is green is prepared using carboxylic acid and the direct addition of alkene to close
At route, atom utilization theoretically can reach 100%, and can simplify process flow, save separating energy consumption, reduce carboxylic
Acid esters production cost, the process route have double dominant economically and environmentally.
Patent US3678099 disclose it is a kind of using sulfonic acid modified ion exchange resin Amberlyst15 as solid acid
The process flow of catalyst acetic acid and isobutene addition esterification.Wherein the molar ratio of isobutene and acetic acid is 1.31:
1；Reaction temperature is 150 DEG C, reaction pressure 3MPa, and the conversion ratio of last acetic acid is 69.1%.Tert-butyl acetate is selectively
77.0%, the selectivity of isobutene dimer is 21.1%.The above method shows that sulfonate resin has very high work to this reaction
Property, but tert-butyl acetate is selectively lower.Patent CN102924272A reports a kind of using MCM-41-SO3H is catalyzed carboxylic acid
With the method for alkene addition lactate synthesis carboxylate, polymerization inhibitor tert-butyl alcohol dosage is accounted under 9.0% reaction condition of acrylic acid quality, most
Whole acrylic acid conversion ratio is 55.0%, and it is 92.6% that tert-butyl acrylate, which generates selectivity,.It is mesoporous employed in the above method
Molecular sieve catalyst is added polymerization inhibitor as the tert-butyl alcohol, leads to the tert-butyl alcohol and two isobutyls to improve the selectivity of carboxylate
Alkene forms azeotropic mixture, increases separating energy consumption and the equipment investment of subsequent product.Heteropoly acid has acidity by force, better heat stability
Feature is widely used in catalytic field.Document [Chinese Journal of Catalysis, 1988, V9 (4): 404-
410] report is applied to reacting for catalyzed alkene and carboxylic acid using by heteropoly acid, and wherein result of study shows when with tungstophosphoric acid
(H3PW12O40·xH2It O is) catalyst 1- butylene with acetic acid when reacting, the conversion ratio of acetic acid can reach after reaction time 7h
To 86%, the selectivity of product has reached 98% or more.Heteropoly acid employed in above-mentioned report is dissolved in reaction system, reactant
Separation with catalyst is difficult.
Summary of the invention
The purpose of the present invention is to provide a kind of order mesoporous C/SiOs group modified using hydramine2Carried heteropoly acid is urged
The method that agent catalyzes and synthesizes carboxylate is soluble in polar solvent to overcome heteropoly acid thermal stability poor, and acid single lacks
Point.
The present invention utilizes the highly acid of heteropoly acid, and adjustable in conjunction with mesoporous material aperture, pore size distribution is uniform, large specific surface area
Feature.Heteropoly acid is fixed on mesoporous material surface using the alkalinity of alcohol amine groups and prepares solid acid catalyst, in roasting process
Middle generation defective bit heteropoly acid, has heteropoly acidIt is acid with Lewis acid, the low specific surface of heteropoly acid is solved, it is readily soluble
In polar solvent, active sites are easy to run off, and acid single disadvantage, the catalyst by modulation acid amount as carboxylate has
High activity and highly selective.
The technical solution adopted in the present invention is as follows:
The first purpose of the invention is to provide a kind of group modified order mesoporous C/SiO of hydramine2Carried heteropoly acid is urged
Agent, the catalyst by dissolving organic formwork agent and hydramine substance in acid condition, after addition silicon source is hydrolyzed,
Heteropoly acid aqueous solution is slowly added dropwise, rear hydrothermal crystallizing is sufficiently stirred, solution filtration washing dry roasting after crystallization is made.
Further, the catalyst is prepared by the following method:
(1) organic formwork agent and hydramine substance are added to H+Concentration in the acidic aqueous solution of 0.5~2.5mol/L,
20~50 DEG C of 1~3h of stirring after being completely dissolved to template and hydramine substance, are added silicon source, stir under aforementioned temperature
0.5~2h；
(2) the heteropoly acid aqueous solution of 0.1~0.5g/mL of mixed solution and dripping in step (1), preferred 0.2g/
mL；At 20~50 DEG C stirring 20~for 24 hours, the mixing suspension obtained after stirring is placed in hydrothermal synthesis kettle in 80~130 DEG C
24~96h of lower crystallization, it is preferred that 48~72h of crystallization at 100 DEG C~120 DEG C；Crystallization mixed solution is taken out after being cooled to room temperature；
(3) after the filtering of step (2) crystallization obtains mixed solution or centrifuge washing, obtained filter cake or solid are placed in
In baking oven, dry 8~12h, obtained solid powder 200~400 DEG C of 4~6h of roasting under inert atmosphere at 50~100 DEG C,
The inert atmosphere can be vacuum, N2, Ar, He, preferably N2；Preferably, 300~350 DEG C of the maturing temperature；It obtains
The group modified order mesoporous C/SiO of hydramine2Carried heteropoly acid catalyst.
Further, the organic formwork agent is also carbon source simultaneously, and the organic formwork agent is selected from non-ionic table
Face activating agent；Preferably polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123, EO20PO70EO20, M
=5800), (F127, EO106PO70EO106, M=12600), (F108, EO132PO50EO132, M=10400)；Preferably P123；
The hydramine substance is selected from monoethanolamine, diethanol amine, triethanolamine；Preferably diethanol amine；
The silicon source is selected from sodium metasilicate, tetraethyl orthosilicate, butyl silicate, silica solution, waterglass, methyl silicate, excellent
It is selected as tetraethyl orthosilicate；
The heteropoly acid is selected from phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, preferably phosphotungstic acid.
Further, the H of the acidic aqueous solution+Concentration is 1~2mol/L；
The acid source of the acidic aqueous solution is hydrochloric acid, nitric acid, phosphoric acid, preferably hydrochloric acid；
The H of the organic formwork agent and acidic aqueous solution+Molar ratio is 0.001:1~0.01:1；It is preferably in a proportion of
0.001:1~0.005:1；
The molar ratio of the organic formwork agent and silicon source is 0.01~0.05:1, preferably 0.01~0.025:1；
The mass ratio of the heteropoly acid and silicon source is 0.05~0.5:1, preferably 0.1~0.4:1；
The mass ratio of the hydramine substance and heteropoly acid is 0.1~1.2:1, preferably 0.2~0.8:1.
A second object of the present invention is to provide the group modified order mesoporous C/SiO of hydramine above-mentioned2Carried heteropoly acid
Application of the catalyst in catalysis carboxylic acid and alkene synthesizing carboxylate.
Third object of the present invention is to provide a kind of group modified order mesoporous C/SiO of hydramine2Carried heteropoly acid is urged
The preparation method of agent, the described method comprises the following steps:
(1) organic formwork agent and hydramine substance are added to H+Concentration in the acidic aqueous solution of 0.5~2.5mol/L,
20~50 DEG C of 1~3h of stirring after being completely dissolved to template and hydramine substance, are added silicon source, stir under aforementioned temperature
0.5~2h；
(2) the heteropoly acid aqueous solution of 0.1~0.5g/mL of mixed solution and dripping in step (1), preferred 0.2g/
mL；At 20~50 DEG C stirring 20~for 24 hours, the mixing suspension obtained after stirring is placed in hydrothermal synthesis kettle in 80~130 DEG C
24~96h of lower crystallization, it is preferred that 48~72h of crystallization at 100 DEG C~120 DEG C；Crystallization mixed solution is taken out after being cooled to room temperature；
(3) after the filtering of step (2) crystallization obtains mixed solution or centrifuge washing, obtained filter cake or solid are placed in
In baking oven, dry 8~12h, obtained solid powder 200~400 DEG C of 4~6h of roasting under inert atmosphere at 50~100 DEG C,
The inert atmosphere can be vacuum, N2, Ar, He, preferably N2；Preferably, 300~350 DEG C of the maturing temperature；It obtains
The group modified order mesoporous C/SiO of hydramine2Carried heteropoly acid catalyst.
Further, the organic formwork agent is also carbon source simultaneously, and the organic formwork agent is selected from non-ionic table
Face activating agent；Preferably polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123, EO20PO70EO20, M
=5800), (F127, EO106PO70EO106, M=12600), (F108, EO132PO50EO132, M=10400)；Preferably P123；
The hydramine substance is selected from monoethanolamine, diethanol amine, triethanolamine；Preferably diethanol amine；
The silicon source is selected from sodium metasilicate, tetraethyl orthosilicate, butyl silicate, silica solution, waterglass, methyl silicate, excellent
It is selected as tetraethyl orthosilicate；
The heteropoly acid is selected from phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, preferably phosphotungstic acid.
Further, the H of the acidic aqueous solution+Concentration is 1~2mol/L；
The acid source of the acidic aqueous solution is hydrochloric acid, nitric acid, phosphoric acid, preferably hydrochloric acid；
The H of the organic formwork agent and acidic aqueous solution+Molar ratio is 0.001:1~0.01:1；It is preferably in a proportion of
0.001:1~0.005:1；
The molar ratio of the organic formwork agent and silicon source is 0.01~0.05:1, preferably 0.01~0.025:1；
The mass ratio of the heteropoly acid and silicon source is 0.05~0.5:1, preferably 0.1~0.4:1；
The mass ratio of the hydramine substance and heteropoly acid is 0.1~1.2:1, preferably 0.2~0.8:1.
Fourth object of the present invention is to provide a kind of order mesoporous C/SiO group modified using hydramine above-mentioned2It is negative
The method that carrying heteropolyacid is catalyzed carboxylic acid and alkene synthesizing carboxylate, the group modified order mesoporous C/SiO of the hydramine2Load
Heteropolyacid catalyst dosage is 0.05wt.%~10wt.% of carboxylic acid quality.
Further, the carboxylic acid be one of straight chain type carboxylic acid, alicyclic carboxylic acid, aromatic carboxylic acid, it is described
Straight chain type carboxylic acid can be selected from formic acid, acetic acid, acrylic acid, propionic acid；
There is no structural requirement, general alkene can be applied the alkene in the present invention, preferably be selected from isobutene, butylene,
Cyclohexene；
The molar ratio of the alkene and carboxylic acid is 6:1~1:1, preferably 4:1~1:1；
The group modified order mesoporous C/SiO of the hydramine2Carried heteropoly acid catalyst dosage is carboxylic acid quality
1wt.%~5wt.%；
Reaction temperature is 30~80 DEG C, preferably 30~50 DEG C；
Reaction pressure is 0.5~1.5MPa (gauge pressure), preferably 0.7~1.2MPa；
Stirring rate is 300~1000r/min, preferably 400~1000r/min, further preferably 600~800r/
min；
Reaction time is 2~12h, preferably 8~12h, further preferably 8~10h.
Pressure described in technical solution of the present invention is gauge pressure.
Beneficial effects of the present invention:
The group modified order mesoporous C/SiO of hydramine of the present invention2Carried heteropoly acid catalyst, by being added in synthesis phase
Alcohol amine groups are regulator, alleviate destruction of the heteropoly acid particle to skeleton, are conducive to carrier ordered cellular structure；It is roasting
The decomposition of alcohol amine groups makes metal oxygen bond rupture in heteropoly acid particle in the process, and catalyst is finally made to have ordered mesoporous pore canals,
Acid site can modulation, haveIt is acid with Lewis acid, it is non-corrosive, it is easily isolated, activated centre not easily runs off, energy
Enough under conditions of higher temperature, not needing addition alkene polymerization inhibitor, high conversion catalyzed alkene and carboxylic acid synthesizing carboxylate are high
Carboxylate is selectively produced, the separating energy consumption and equipment investment cost of reaction product can be reduced simultaneously.It is mild with reaction condition,
The advantages that by-product is few, environmentally protective, reduces production cost.
Detailed description of the invention
Fig. 1 is the small angle x-ray diffraction (SAXD) spectrogram of 1 gained catalyst of Examples 1 to 5 and comparative example.
Fig. 2 is the N of catalyst obtained by Examples 1 to 52Adsorption/desorption curve spectrogram
Fig. 3 is the pyridine infrared spectrogram of catalyst obtained by Examples 1 to 5.
Fig. 4 is that the TEM of 3 gained catalyst of embodiment schemes.
Specific embodiment
Below with reference to embodiment, the present invention will be further described, is the experiment that actual conditions are not specified in the following example
Method, usually according to the known approaches of this field.
In the present invention program, the conversion ratio calculation formula are as follows: conversion ratio=(amount/raw material of the raw material converted is total
Amount) × 100%
In the present invention program, the selectivity calculation formula are as follows: selectivity=(be converted into raw material consumed by purpose product
The amount of the raw material measure/converted) × 100%
Embodiment 1
By 9g P123,0.5g diethanol amine, 360mL 2mol/L hydrochloric acid is sequentially added in three-necked flask, is stirred at 40 DEG C
1~3h is mixed, 24.48g tetraethyl orthosilicate (TEOS, the present embodiment P123 is added after dissolving P123 and diethanol amine thoroughly
It is 0.013:1 with TEOS molar ratio), 30min is stirred at 40 DEG C, and the 0.2g/mL silico-tungstic acid water of 12.25mL is then slowly added dropwise
Solution, (i.e. 2.45g silico-tungstic acid), uniform stirring for 24 hours, put into polytetrafluoro by mixing suspension after mixing evenly at 40 DEG C
In the stainless steel water thermal synthesis kettle of ethylene liner, after 100 DEG C crystallization 2 days (48h), be cooled to room temperature, by after crystallization it is solid-
Filter cake is placed in baking oven in 50 DEG C of dry 8~12h, by the article after drying in nitrogen atmosphere by liquid two-phase mixture filtration washing
It encloses, roasts 6h at 300 DEG C.Obtain the group modified order mesoporous C/SiO of required hydramine2Carried heteropoly acid catalyst is denoted as
0.1HSiW-0.2DEA@C/SiO2(TEOS) -300-P123 (wherein 0.1 refers to silico-tungstic acid and tetraethyl orthosilicate mass ratio, 0.2
Refer to diethanol amine and silico-tungstic acid mass ratio, 300 be maturing temperature).From the small angle x-ray diffraction (SAXD) spectrogram of catalyst (see attached drawing
1) it can be seen that, occur the characteristic peak in orderly duct at 0.7 in, illustrate that catalyst duct is ordered structure.Utilize N2Adsorption desorption
Physical means are analyzed catalyst cellular structure the catalyst n that synthesis is found (see attached drawing 2)2Adsorption desorption isothermal curve is
The IVth class nitrogen adsorption desorption curve type for possessing H1 type lag winding illustrates that the catalyst possesses uniform mesoporous of pore size
Cellular structure.TEM intuitively reflects the order (see attached drawing 4) in duct.
Embodiment 2
By 9gP123,1g diethanol amine, 360mL 2mol/L hydrochloric acid is sequentially added in three-necked flask, is stirred at 40 DEG C
1~3h, make P123 and diethanol amine thoroughly dissolve after be added 24.48g tetraethyl orthosilicate (TEOS, the present embodiment P123 with
TEOS molar ratio is 0.013:1), 30min is stirred at 40 DEG C, the 0.2g/mL phosphotungstic acid that 24.5mL is then slowly added dropwise is water-soluble
Liquid, (i.e. 4.90g phosphotungstic acid), uniform stirring for 24 hours, is put mixing suspension after mixing evenly with polytetrafluoro at 40 DEG C
In the stainless steel water thermal synthesis kettle of ethylene liner, after 100 DEG C crystallization 2 days (48h), be cooled to room temperature, by after crystallization it is solid-
Filter cake is placed in baking oven in 50 DEG C of dry 8~12h, the article after drying is placed on horse by liquid two-phase mixture filtration washing
Not 6h is roasted at nitrogen atmosphere, 300 DEG C in furnace.Obtain the group modified order mesoporous C/SiO of required hydramine2Carried heteropoly acid
Catalyst is denoted as 0.2HPW-0.2DEA@C/SiO2(TEOS) (wherein 0.2 refers to phosphotungstic acid and tetraethyl orthosilicate to -300-P123
Mass ratio, 0.2 refers to diethanol amine and phosphotungstic acid mass ratio, and 300 be maturing temperature).Pyridine is infrared to show that hydramine is group modified
Order mesoporous C/SiO2Carried heteropoly acid catalyst hasIt is acid with Lewis acid.(Fig. 3)
Embodiment 3
By 21g F127,4.52g diethanol amine, 360mL 2mol/L hydrochloric acid is sequentially added in three-necked flask, at 40 DEG C
Stir 1~3h, make P123 and diethanol amine thoroughly dissolve after be added 37.66g butyl silicate (TBOS, the present embodiment F127 and
TBOS molar ratio is 0.014:1), 30min is stirred at 40 DEG C, the 0.2g/mL phosphotungstic acid that 37.65mL is then slowly added dropwise is water-soluble
Liquid, (i.e. 7.53g phosphotungstic acid), uniform stirring for 24 hours, is put mixing suspension after mixing evenly with polytetrafluoro at 40 DEG C
In the stainless steel water thermal synthesis kettle of ethylene liner, after 100 DEG C crystallization 2 days (48h), be cooled to room temperature, by after crystallization it is solid-
Filter cake is placed in baking oven in 50 DEG C of dry 8~12h, the article after drying is placed on horse by liquid two-phase mixture filtration washing
Not 6h is roasted at nitrogen atmosphere, 300 DEG C in furnace.Obtain the group modified order mesoporous C/SiO of required hydramine2Carried heteropoly acid
Catalyst is denoted as 0.2HPW-0.6DEA@C/SiO2(TBOS) (wherein 0.2 refers to phosphotungstic acid and tetraethyl orthosilicate to -300-F127
Mass ratio, 0.6 refers to diethanol amine and phosphotungstic acid mass ratio, and 300 be maturing temperature) TEM phenogram such as Fig. 4 institute of gained catalyst
Show.
Embodiment 4
By 9g P123,6g monoethanolamine, 360mL 2mol/L hydrochloric acid is sequentially added in three-necked flask, is stirred at 40 DEG C
37.66g butyl silicate (TBOS, the present embodiment P123 and TBOS is added after dissolving P123 and monoethanolamine thoroughly in 1~3h
Molar ratio is 0.013:1), 30min is stirred at 40 DEG C, the 0.2g/mL phosphotungstic acid aqueous solution of 75mL is then slowly added dropwise, (i.e.
15g phosphotungstic acid), uniform stirring for 24 hours, is put mixing suspension after mixing evenly with polytetrafluoroethyllining lining at 40 DEG C
Stainless steel water thermal synthesis kettle in, after 100 DEG C crystallization 2 days (48h), be cooled to room temperature, the solid-liquid two-phase after crystallization mixed
Close object filtration washing, filter cake be placed in baking oven in 50 DEG C of dry 8~12h, by the article after drying be placed in Muffle furnace in
Nitrogen atmosphere roasts 6h at 400 DEG C.Obtain the group modified order mesoporous C/SiO of required hydramine2Carried heteropoly acid catalyst,
It is denoted as 0.4HPW-0.4MEA@C/SiO2(TBOS) (wherein 0.4 refers to phosphotungstic acid and butyl silicate mass ratio to -400-P123, and 0.6 refers to
Monoethanolamine and phosphotungstic acid mass ratio, 400 be maturing temperature).
Embodiment 5
By 21g F127,4.90g triethanolamine, 360mL 2mol/L hydrochloric acid is sequentially added in three-necked flask, at 40 DEG C
1~3h is stirred, 24.48g tetraethyl orthosilicate (TEOS, the present embodiment is added after dissolving P123 and triethanolamine thoroughly
F127 and TEOS molar ratio are 0.014:1), 30min is stirred at 40 DEG C, and the 0.2g/mL phosphorus tungsten of 24.5mL is then slowly added dropwise
Aqueous acid, (i.e. 4.90g phosphotungstic acid), uniform stirring for 24 hours, is put mixing suspension after mixing evenly into and is had at 40 DEG C
In the stainless steel water thermal synthesis kettle of polytetrafluoroethyllining lining, after 100 DEG C crystallization 2 days (48h), it is cooled to room temperature, by crystallization
Filter cake is placed in baking oven in 50 DEG C of dry 8~12h, the article after drying is put by solid-liquid two-phase mixture filtration washing afterwards
It sets and roasts 6h at 300 DEG C in Muffle furnace.Obtain the group modified order mesoporous C/SiO of required hydramine2Carried heteropoly acid is urged
Agent is denoted as 0.2HPW-1TEA@C/SiO2(TEOS) (wherein 0.2 refers to phosphotungstic acid and tetraethyl orthosilicate quality to -300-F127
Than 1 refers to triethanolamine and phosphotungstic acid mass ratio, and 300 be maturing temperature).
Embodiment 6
By 74g propionic acid, the 0.1HSiW-0.2DEA@C/SiO of 0.74g embodiment 12(TEOS) -300-P123 is added to
In the intermittent titanium autoclave of 300mL, it is subsequently passed 112g isobutene (isobutene is 2:1 with propionic acid molar ratio), reaction temperature
30 DEG C, being passed through nitrogen makes pressure in kettle rise to 1MPa, under the conditions of speed of agitator is 600r/min, reaction 10h.It is adopted by sampling pipe
Collect reaction solution, then by centrifugation removal catalyst, is analyzed followed by gas chromatograph, Analysis result calculation obtains third
Sour conversion ratio is 90%, and propanoic acid tert-butyl ester is selectively 96%, and diisobutylene is selectively 1.4%.
Embodiment 7
By 60g acetic acid, the 0.2HPW-0.2DEA@C/SiO of 0.6g embodiment 22(TEOS) -300-P123 is added to 300mL
In intermittent titanium autoclave, 82g cyclohexene (cyclohexene is 1:1 with acetic acid molar ratio) is then added, 80 DEG C of reaction temperature, stirs
Revolving speed is mixed to react 10h under the conditions of 600r/min.Reaction solution is acquired by sampling pipe, catalyst is then removed by centrifugation, with
It is analyzed afterwards using gas chromatograph, it is 92% that Analysis result calculation, which obtains acetic acid conversion ratio, and cyclohexyl acetate is selectively
99%.
Embodiment 8
By 60g acetic acid, the 0.2HPW-0.2DEA@C/SiO of 0.6g embodiment 22(TEOS) -300-P123 is added to 300mL
In intermittent titanium autoclave, it is subsequently passed 112g isobutene (isobutene is 2:1 with acetic acid molar ratio), in reaction temperature 30
DEG C, being passed through nitrogen makes pressure in kettle rise to 1MPa, under the conditions of speed of agitator is 600r/min, reaction 10h.It is acquired by sampling pipe
Reaction solution is analyzed, Analysis result calculation obtains acetic acid then by centrifugation removal catalyst followed by gas chromatograph
Conversion ratio is 92%, and tert-butyl acetate is selectively 96%, and diisobutylene is selectively 1.7%.
Embodiment 9
By 60g acetic acid, the 0.2HPW-0.6DEA@C/SiO of 0.6g embodiment 32(TBOS) -300-F127 is added to 300mL
In intermittent titanium autoclave, it is subsequently passed 112g isobutene (isobutene is 2:1 with acetic acid molar ratio), in reaction temperature 40
DEG C, being passed through nitrogen makes pressure in kettle rise to 1MPa, under the conditions of speed of agitator is 600r/min, reaction 10h.It is acquired by sampling pipe
Reaction solution is analyzed, Analysis result calculation obtains acetic acid then by centrifugation removal catalyst followed by gas chromatograph
Conversion ratio is 95%, and tert-butyl acetate is selectively 95%, and diisobutylene is selectively 2.9%.
Embodiment 10
By 46g formic acid, the 0.2HPW-0.6DEA@C/SiO of 0.46g embodiment 32(TBOS) -300-F127 is added to
In the intermittent titanium autoclave of 300mL, it is subsequently passed 82g cyclohexene (cyclohexene is 1:1 with formic acid molar ratio), in reaction temperature
70 DEG C of degree reacts 10h under the conditions of speed of agitator is 600r/min.Reaction solution is acquired by sampling pipe, then passes through centrifugation removal
Catalyst is analyzed followed by gas chromatograph, and it is 86% that Analysis result calculation, which obtains formic acid conversion ratio, cyclohexyl formate
Selectivity is 99%.
Embodiment 11
By 72g acrylic acid, the 0.4HPW-0.4MEA@C/SiO of 0.72g embodiment 42(TBOS) -400-P123 is added to
In the intermittent titanium autoclave of 300mL, it is subsequently passed 112g isobutene (isobutene is 2:1 with acrylic acid molar ratio), is being reacted
40 DEG C of temperature, being passed through nitrogen makes pressure in kettle rise to 1MPa, under the conditions of speed of agitator is 600r/min, reaction 10h.Pass through sampling
Pipe acquires reaction solution, then by centrifugation removal catalyst, is analyzed followed by gas chromatograph, Analysis result calculation obtains
It is 91% to acrylic acid conversion ratio, tert-butyl acrylate is selectively 94%, and diisobutylene is selectively 3.1%.
Embodiment 12
By 72g acrylic acid, the 0.4HPW-0.4MEA@C/SiO of 0.72g embodiment 42(TBOS) -400-P123 is added to
In the intermittent titanium autoclave of 300mL, 82g cyclohexene (cyclohexene is 1:1 with acrylic acid molar ratio) is then added, in reaction temperature
80 DEG C of degree reacts 10h under the conditions of speed of agitator is 600r/min.Reaction solution is acquired by sampling pipe, then passes through centrifugation removal
Catalyst is analyzed followed by gas chromatograph, and it is 95% that Analysis result calculation, which obtains acrylic acid conversion ratio, acrylic acid ring
Own ester is selectively 99%.
Embodiment 13
By 60g acetic acid, the 0.2HPW-1TEA@C/SiO of 0.6g embodiment 52(TEOS) -300-F127 is added to 300mL
In intermittent titanium autoclave, 112g isobutene (isobutene is 2:1 with acetic acid molar ratio) is then added, in reaction temperature 30
DEG C, being passed through nitrogen makes pressure in kettle rise to 1MPa, under the conditions of speed of agitator is 600r/min, reaction 10h.It is acquired by sampling pipe
Reaction solution is analyzed, Analysis result calculation obtains acetic acid then by centrifugation removal catalyst followed by gas chromatograph
Conversion ratio is 92%, and tert-butyl acetate is selectively 95%.
Embodiment 14
By 74g propionic acid, the 0.2HPW-1TEA@C/SiO of 0.74g embodiment 52(TEOS) -300-F127 is added to 300mL
In intermittent titanium autoclave, 112g isobutene (isobutene is 2:1 with propionic acid molar ratio) is then added, in reaction temperature 30
DEG C, being passed through nitrogen makes pressure in kettle rise to 1MPa, under the conditions of speed of agitator is 600r/min, reaction 10h.It is acquired by sampling pipe
Reaction solution is analyzed, Analysis result calculation obtains acetic acid then by centrifugation removal catalyst followed by gas chromatograph
Conversion ratio is 89%, and tert-butyl acetate is selectively 97%.
Embodiment 15
The present embodiment is divided into 7 groups, investigates different catalyst samples of the invention respectively to carboxylic acid under different condition and alkene
Catalytic reaction effect.Concrete operations are as follows:
1, the group modified order mesoporous C/SiO of hydramine2Carried heteropoly acid catalyst preparation:
By 9g P123, the hydramine of different quality, 360mL 2mol/L hydrochloric acid is sequentially added in three-necked flask, at 40 DEG C
1~3h is stirred, 24.48g tetraethyl orthosilicate (TEOS) is added after dissolving P123 and hydramine thoroughly, is stirred at 40 DEG C
30min is then respectively adding the phosphotungstic acid (phosphotungstic acid aqueous solution is slowly added dropwise) of different quality, the uniform stirring at 40 DEG C
For 24 hours, mixing suspension after mixing evenly is put into the stainless steel water thermal synthesis kettle with polytetrafluoroethyllining lining, 100
DEG C after crystallization 2 days (48h), it is cooled to room temperature, by the solid-liquid two-phase mixture filtration washing after crystallization, filter cake is placed in baking
In 50 DEG C of dry 8~12h in case, the article after drying is placed in Muffle furnace and roasts 6h at nitrogen atmosphere, 300 DEG C.Point
The group modified order mesoporous C/SiO of hydramine needed for not obtaining 7 kinds2Carried heteropoly acid catalyst is denoted as 0.1HPW-0.8DEA@
C/SiO2(TEOS)-300-P123、0.2HPW-0.4DEA@C/SiO2(TEOS)-300-P123、 0.3HPW-0.6MEA@C/
SiO2(TEOS)-300-P123、0.3HPW-0.2TEA@C/SiO2(TEOS)-300-P123、 0.4HPW-0.8DEA@C/SiO2
(TEOS)-300-P123、0.4HPW-0.8MEA@C/SiO2(TEOS)-300-P123、 0.2HPW-0.6MEA@C/SiO2
(TEOS) -300-P123 can specify raw material, the ratio of each catalyst of the present embodiment according to the naming rule of Examples 1 to 5.
2, it is catalyzed carboxylic acid and alkene produces carboxylate:
By different quality carboxylic acid, the above-mentioned catalyst of carboxylic acid quality 1wt% is added separately to the intermittent titanium high pressure of 300mL
In kettle, different quality alkene is then added, and (when reactant is isobutene, being passed through nitrogen makes pressure in kettle rise to 1Mpa；Reactant
Pressure is normal pressure when for cyclohexene), under the conditions of speed of agitator is 600r/min, react 10h.Reaction solution is acquired by sampling pipe,
Then by centrifugation removal catalyst, analyzed with gas chromatograph.
Catalyst preparation, carboxylic acid, olefine reaction condition and Analysis result calculation are as shown in table 1.
Table 1:
Embodiment 16
By 60g acetic acid, the 0.2HPW-0.2DEA@C/SiO of 0.6g embodiment 22(TEOS) -300-P123 is added to 300mL
In intermittent titanium autoclave, it is subsequently passed 112g isobutene (isobutene is 2:1 with acetic acid molar ratio), in reaction temperature 30
DEG C, being passed through nitrogen makes pressure in kettle rise to 1MPa, under the conditions of speed of agitator is 600r/min, reaction 10h.It is acquired by sampling pipe
Reaction solution is analyzed then by centrifugation removal catalyst followed by gas chromatograph.Simultaneously by post catalyst reaction recycling
After ethanol washing filtration drying, above-mentioned condition reaction is repeated.Reusability the result is as follows:
The results show that the order mesoporous C/SiO that hydramine prepared by the present invention is group modified2Carried heteropoly acid catalyst is easy to
Separation solves the solubility problem of heteropoly acid, and has still maintained preferable catalytic activity after separating, and realizes multiplicating
It uses.
Comparative example 1
By 9g P123,360mL 2mol/L hydrochloric acid is sequentially added in three-necked flask, and 1~3h is stirred at 40 DEG C, is made
P123 be added after thoroughly dissolving 24.48g tetraethyl orthosilicate (TEOS, the present embodiment P123 and TEOS molar ratio are 0.013:
1) 30min, is stirred at 40 DEG C, and the 0.2g/mL phosphotungstic acid aqueous solution of 24.5mL is then slowly added dropwise, (i.e. 4.90g phosphotungstic acid),
Uniform stirring for 24 hours, puts mixing liquid after mixing evenly into the stainless steel hydro-thermal with polytetrafluoroethyllining lining at 40 DEG C
In synthesis reactor, after 100 DEG C crystallization 2 days (48h), it is cooled to room temperature, the solid-liquid two-phase mixture after crystallization is crossed into diafiltration
It washs, filter cake is placed in baking oven in 50 DEG C of dry 8~12h, the article after drying is placed in Muffle furnace in pure oxygen atmosphere,
6h is roasted at 300 DEG C.Required loaded by heteropoly acid mesopore silicon oxide catalyst is obtained, 0.2HPW@/SiO is denoted as2(TEOS)-300-
P123 (wherein 0.2 refers to phosphotungstic acid and tetraethyl orthosilicate mass ratio, and 300 be maturing temperature).
By 60g acetic acid, the 0.2HPW@SiO of this comparative example of 0.6g preparation2(TEOS) -300-P123 is added to 300mL interval
In formula titanium autoclave, it is subsequently passed 112g isobutene (isobutene is 2:1 with acetic acid molar ratio), at 30 DEG C of reaction temperature, is led to
Entering nitrogen makes pressure in kettle rise to 1MPa, under the conditions of speed of agitator is 600r/min, reaction 10h.It is acquired and is reacted by sampling pipe
Liquid is analyzed then by centrifugation removal catalyst followed by gas chromatograph, and Analysis result calculation obtains acetic acid conversion
Rate is 79%, and tert-butyl acetate is selectively 91%, and diisobutylene is selectively 5.7%.
Show under the identical conditions such as catalyst amount with the comparison of embodiment 8, group modified order mesoporous of hydramine
C/SiO2Carried heteropoly acid catalyst effectively improves the conversion ratio and carboxylate selectivity of carboxylic acid.
Comparative example 2
By 9g P123,360mL 2mol/L hydrochloric acid sequentially adds in three-necked flask, stirs at 40 DEG C, keeps P123 thorough
Dissolution after be added 24.48g tetraethyl orthosilicate (TEOS), at 40 DEG C uniform stirring for 24 hours, mixed liquor after mixing evenly
Body is put into the stainless steel water thermal synthesis kettle with polytetrafluoroethyllining lining, after crystallization 1 day, is cooled to room temperature at 100 DEG C, will
Filter cake is placed in baking oven in 50 DEG C of dryings, the article after drying is placed by the solid-liquid two-phase mixture filtration washing after crystallization
6h is roasted at nitrogen atmosphere, 300 DEG C in Muffle furnace.Catalyst is obtained, C/SiO is denoted as2(TEOS) -300-P123 is (wherein
300 be maturing temperature).
60g acetic acid, 1.2g catalyst C/SiO are added in the intermittent titanium autoclave of 300mL2(TEOS) -300-P123,
It is passed through 112g isobutene (isobutene is 2:1 with acetic acid molar ratio), 40 DEG C is heated to, is forced into 1MPa, be in speed of agitator
Under the conditions of 600r/min, 10h is reacted.Liquid phase reactor liquid is acquired, is carried out after centrifuge separation removal catalyst using gas chromatograph
Analysis, analysis is the result shows that acetic acid and isobutene unreacted.
I.e. without the C/SiO of loaded by heteropoly acid2The addition reaction catalytically inactive of catalyst Dichlorodiphenyl Acetate and isobutene.
Claims (10)
1. a kind of group modified order mesoporous C/SiO of hydramine2Carried heteropoly acid catalyst, which is characterized in that the catalyst is logical
It crosses and dissolves organic formwork agent and hydramine substance in acidic aqueous solution, after addition silicon source is hydrolyzed, heteropoly acid is slowly added dropwise
Rear hydrothermal crystallizing is sufficiently stirred in aqueous solution, and solution filtration washing dry roasting after crystallization is made.
2. the group modified order mesoporous C/SiO of hydramine according to claim 12Carried heteropoly acid catalyst, feature exist
In the catalyst is prepared by the following method:
(1) organic formwork agent and hydramine substance are added to H+Concentration in the acidic aqueous solution of 0.5~2.5mol/L, 20~
50 DEG C of 1~3h of stirring, after being completely dissolved to template and hydramine substance, be added silicon source, under aforementioned temperature stir 0.5~
2h；
(2) the heteropoly acid aqueous solution of 0.1~0.5g/mL of mixed solution and dripping in step (1), preferred 0.2g/mL；?
At 20~50 DEG C stirring 20~for 24 hours, the mixing suspension obtained after stirring is placed in hydrothermal synthesis kettle the crystallization at 80~130 DEG C
24~96h, it is preferred that 48~72h of crystallization at 100 DEG C~120 DEG C；Crystallization mixed solution is taken out after being cooled to room temperature；
(3) after the filtering of step (2) crystallization obtains mixed solution or centrifuge washing, obtained filter cake or solid are placed in baking oven
In, dry 8~12h at 50~100 DEG C, obtained solid powder 200~400 DEG C of roasting 4~6h under inert atmosphere are described
Inert atmosphere can be vacuum, N2, Ar, He, preferably N2；Preferably, 300~350 DEG C of the maturing temperature；Obtain hydramine
Group modified order mesoporous C/SiO2Carried heteropoly acid catalyst.
3. the group modified order mesoporous C/SiO of hydramine according to claim 1 or 22Carried heteropoly acid catalyst, it is special
Sign is,
The organic formwork agent is selected from nonionic surface active agent；Preferably P123, F127, F108；More preferably P123；
The hydramine substance is selected from monoethanolamine, diethanol amine, triethanolamine；Preferably diethanol amine；
The silicon source is selected from sodium metasilicate, tetraethyl orthosilicate, butyl silicate, silica solution, waterglass, methyl silicate, preferably
Tetraethyl orthosilicate；
The heteropoly acid is selected from phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, preferably phosphotungstic acid.
4. the group modified order mesoporous C/SiO of hydramine according to claim 1 or 22Carried heteropoly acid catalyst, it is special
Sign is,
The H of the acidic aqueous solution+Concentration is 1~2mol/L；
The acid source of the acidic aqueous solution is hydrochloric acid, nitric acid, phosphoric acid, preferably hydrochloric acid；
The H+ molar ratio of the organic formwork agent and acidic aqueous solution is 0.001:1~0.01:1；It is preferably in a proportion of 0.001:1
~0.005:1；
The molar ratio of the organic formwork agent and silicon source is 0.01~0.05:1, preferably 0.01~0.025:1；
The mass ratio of the heteropoly acid and silicon source is 0.05~0.5:1, preferably 0.1~0.4:1；
The mass ratio of the hydramine substance and heteropoly acid is 0.1~1.2:1, preferably 0.2~0.8:1.
5. the group modified order mesoporous C/SiO of the described in any item hydramine of Claims 1-42Carried heteropoly acid catalyst is being urged
Change the application in carboxylic acid and alkene synthesizing carboxylate.
6. a kind of group modified order mesoporous C/SiO of hydramine2The preparation method of carried heteropoly acid catalyst, which is characterized in that institute
State method the following steps are included:
(1) organic formwork agent and hydramine substance are added to H+Concentration in the acidic aqueous solution of 0.5~2.5mol/L, 20~
50 DEG C of 1~3h of stirring, after being completely dissolved to template and hydramine substance, be added silicon source, under aforementioned temperature stir 0.5~
2h；
(2) the heteropoly acid aqueous solution of 0.1~0.5g/mL of mixed solution and dripping in step (1), preferred 0.2g/mL；?
At 20~50 DEG C stirring 20~for 24 hours, the mixing suspension obtained after stirring is placed in hydrothermal synthesis kettle the crystallization at 80~130 DEG C
24~96h, it is preferred that 48~72h of crystallization at 100 DEG C~120 DEG C；Crystallization mixed solution is taken out after being cooled to room temperature；
(3) after the filtering of step (2) crystallization obtains mixed solution or centrifuge washing, obtained filter cake or solid are placed in baking oven
In, dry 8~12h at 50~100 DEG C, obtained solid powder 200~400 DEG C of roasting 4~6h under inert atmosphere are described
Inert atmosphere can be vacuum, N2, Ar, He, preferably N2；Preferably, 300~350 DEG C of the maturing temperature；Obtain hydramine
Group modified order mesoporous C/SiO2Carried heteropoly acid catalyst.
7. the group modified order mesoporous C/SiO of hydramine according to claim 62The preparation side of carried heteropoly acid catalyst
Method, which is characterized in that
The organic formwork agent is selected from nonionic surface active agent；Preferably P123, F127, F108；More preferably P123；
The hydramine substance is selected from monoethanolamine, diethanol amine, triethanolamine；Preferably diethanol amine；
The silicon source is selected from sodium metasilicate, tetraethyl orthosilicate, butyl silicate, silica solution, waterglass, methyl silicate, preferably
Tetraethyl orthosilicate；
The heteropoly acid is selected from phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid, preferably phosphotungstic acid.
8. the group modified order mesoporous C/SiO of hydramine according to claim 62The preparation side of carried heteropoly acid catalyst
Method, which is characterized in that
The H of the acidic aqueous solution+Concentration is 1~2mol/L；
The acid source is hydrochloric acid, nitric acid, phosphoric acid, preferably hydrochloric acid；
The H of the organic formwork agent and acidic aqueous solution+Molar ratio is 0.001:1~0.01:1；It is preferably in a proportion of 0.001:1
~0.005:1；
The molar ratio of the organic formwork agent and silicon source is 0.01~0.05:1, preferably 0.01~0.025:1；
The mass ratio of the heteropoly acid and silicon source is 0.05~0.5:1, preferably 0.1~0.4:1；
The mass ratio of the hydramine substance and heteropoly acid is 0.1~1.2:1, preferably 0.2~0.8:1.
9. a kind of order mesoporous C/SiO group modified using the described in any item hydramine of Claims 1-4 42Carried heteropoly acid is urged
Change the method for carboxylic acid and alkene synthesizing carboxylate, which is characterized in that the group modified order mesoporous C/SiO of the hydramine2It is negative
Carrying heteropolyacid catalyst dosage is 0.05wt.%~10wt.% of carboxylic acid quality.
10. the group modified order mesoporous C/SiO of hydramine according to claim 92Carried heteropoly acid is catalyzed carboxylic acid and alkene
The method of synthesizing carboxylate, which is characterized in that
The carboxylic acid is one of straight chain type carboxylic acid, alicyclic carboxylic acid, aromatic carboxylic acid, and the straight chain type carboxylic acid is optional
From formic acid, acetic acid, acrylic acid, propionic acid；
The molar ratio of the alkene and carboxylic acid is 6:1~1:1, preferably 4:1~1:1；
The group modified order mesoporous C/SiO of the hydramine2Carried heteropoly acid catalyst dosage be carboxylic acid quality 1wt.%~
5wt.%；
Reaction temperature is 30~80 DEG C, preferably 30~50 DEG C；
Reaction pressure is 0.5~1.5MPa, preferably 0.7~1.2MPa；
Stirring rate is 300~1000r/min, preferably 400~1000r/min, further preferably 600~800r/min；
Reaction time is 2~12h, preferably 8~12h, further preferably 8~10h.
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