CN107662937A - A kind of order mesoporous barium hydroxide catalyst and its application in the preparation of the pentanediol mono isobutyrate of 2,2,4 trimethyl 1,3 - Google Patents
A kind of order mesoporous barium hydroxide catalyst and its application in the preparation of the pentanediol mono isobutyrate of 2,2,4 trimethyl 1,3 Download PDFInfo
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- CN107662937A CN107662937A CN201610621929.5A CN201610621929A CN107662937A CN 107662937 A CN107662937 A CN 107662937A CN 201610621929 A CN201610621929 A CN 201610621929A CN 107662937 A CN107662937 A CN 107662937A
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- catalyst
- barium
- order mesoporous
- barium hydroxide
- trimethyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 title claims abstract description 34
- 229910001863 barium hydroxide Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 9
- ARFDIYMUJAUTDK-UHFFFAOYSA-N 1-hydroxypentyl 2-methylpropanoate Chemical compound CCCCC(O)OC(=O)C(C)C ARFDIYMUJAUTDK-UHFFFAOYSA-N 0.000 title abstract 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 229910052788 barium Inorganic materials 0.000 claims abstract description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000009833 condensation Methods 0.000 claims abstract description 3
- 230000005494 condensation Effects 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 238000000944 Soxhlet extraction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims description 5
- -1 iso-butane aldehyde Chemical class 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- 235000013847 iso-butane Nutrition 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N trimethylmethane Natural products CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- VPJOGDPLXNTKAZ-UHFFFAOYSA-N 2-methylpropanoic acid;2,2,4-trimethylpentane-1,3-diol Chemical class CC(C)C(O)=O.CC(C)C(O)C(C)(C)CO VPJOGDPLXNTKAZ-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- VHWJJZNDOFZBDW-UHFFFAOYSA-N CC1(C(C(=O)O)C=CC(=C1C(=O)O)C)C Chemical compound CC1(C(C(=O)O)C=CC(=C1C(=O)O)C)C VHWJJZNDOFZBDW-UHFFFAOYSA-N 0.000 description 1
- 229910001051 Magnalium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 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
- 230000007613 environmental effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000005605 isobutyric acids Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of order mesoporous barium hydroxide catalyst and its application in the preparation of the pentanediol mono isobutyrate of 2,2,4 trimethyl 1,3.The catalyst is using barium nitrate as barium source, after weak base prehydrolysis, in the presence of surfactant, forms meso-hole structure, in the presence of a strong base, forms the structure of order mesoporous barium hydroxide finally.The order mesoporous solid barium hydroxide catalyst efficiently isobutylaldehyde condensation can prepare the pentanediol mono isobutyrate of 2,2,4 trimethyl 1,3, and the conversion ratio of isobutylaldehyde and 2, the pentanediol mono isobutyrate of 2,4 trimethyl 1,3 selectivity is up to more than 85%.Compared with traditional barium hydroxide catalyst, the ratio surface of the catalyst is high, and usage amount is low, good hydrothermal stability, the service life length of catalyst.
Description
Technical field
The present invention relates to chemical field, specifically a kind of order mesoporous barium hydroxide catalyst and its 2,2,
Application in the preparation of 4- trimethyl -1,3- pentanediol mono isobutyrates.
Background technology
2,2,4- trimethyl -1,3- pentanediol mono isobutyrates, also known as alcohol ester 12, it is a kind of higher boiling, low freezing point
Water-insoluble binary alcohol esters, itself is nontoxic, has extraordinary picture dissolubility with multi-solvents, is that universally recognized green is molten
Agent, it can directly or indirectly be used as coating additive, lubricant, insecticide, solvent, herbicide, polyester resin and plastic additive
Deng.In recent years, increasingly strict with legislations of environmental protection, the application of the product is more and more extensive.
1,3- glycol and trimethyl -1, the 3- pentanediol list isobutyl of their monoesters product such as 2,2,4- are prepared from corresponding aldehyde
Acid esters, existing many synthetic methods.These methods include indirect synthesis technique and direct synthesis technique.Indirect synthesis technique is in weak acid
Under the conditions of, existing isobutylaldehyde autohemagglutination forms trimerization isobutylaldehyde, and then trimerization isobutylaldehyde is hydrogenated with to form 2,2,4- trimethyls -1,3- penta
Glycol (TMPD) and isobutanol, TMPD are esterified to obtain with isobutyric acid again.But the route complex process, consumption of raw materials is big, is not suitable for
Large-scale production.Direct synthesis technique be isobutylaldehyde in the presence of catalyst, isobutylaldehyde is condensed as 2 first, 2,4- trimethyl -1,
3- pentanediol mono isobutyrates, then further react with isobutylaldehyde to obtain product.This method technique simply invest it is small, but exist
The problem of side reaction is more.The catalyst on direct synthesis technique is mainly base catalyst at present.Such as patent CN 1417195A
In disclose it is a kind of utilize barium hydroxide be catalyst synthetic method.A kind of utilization is disclosed in the A of patent CN 101863762
The method that stratiform magnalium anionic clay prepares alcohol ester 12 for the two-step method of catalyst.
But catalyst used so far is all commercialized barium hydroxide, its specific surface area is small, and structure is irregular,
It can play that the component of catalytic action is few, therefore the quality of the catalyst required for its in course of reaction is more, time length.And utilize barium
It is fast that salt precipitation prepares the method for barium hydroxide its settling velocity, it is more difficult to forms orderly meso-hole structure.Therefore new method is developed
Preparing order mesoporous barium hydroxide becomes challenge.
The content of the invention
The present invention provides a kind of preparation method of the catalyst of order mesoporous barium hydroxide, present invention utilizes weak base, by force
The method of alkali two-step hydrolysis precipitation so that barium salt can prehydrolysis and in the presence of surfactant first, formed orderly
Meso-hole structure, and finally give order mesoporous barium hydroxide.Under the catalyst action, the conversion ratio of isobutylaldehyde and 2,2,4- tri-
Methyl isophthalic acid, 3- pentanediol mono isobutyrates selectivity is up to more than 90%.
According to the present invention, the order mesoporous barium hydroxide is using barium nitrate as barium source, by weak base, highly basic two-step hydrolysis,
In the presence of surfactant, the structure of order mesoporous barium hydroxide is formed.
According to the present invention, the order mesoporous barium hydroxide can be prepared as follows：
Enter surfactant and water in flask, after stirring, be added dropwise to the aqueous solution of barium nitrate, be heated to 30-60
DEG C, preferably 35 DEG C, add ammoniacal liquor stirring, preferably mixing time 1-12h, 6h.The aqueous solution of highly basic is added dropwise to, is acutely stirred
Mix 1-12h, preferably 6h.Filtering, soxhlet extraction utilize with ethanol, washing 24-72 hours, both order mesoporous hydroxide
Barium.
According to the present invention, the surfactant is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride,
OTAC, one kind in Cetyltrimethylammonium bromide.
According to the present invention, the mass ratio that surfactant and water are entered in the flask is 1:3-1:50, preferably 1：20.Institute
The mass fraction of the aqueous solution barium nitrate for the barium nitrate stated is 1-20%.
According to the present invention, the quality of the addition ammoniacal liquor is 1-5 times, preferably 5 times of barium nitrate quality.
According to the present invention, the highly basic of the addition can be sodium hydroxide, potassium hydroxide, cesium hydroxide, in lithium hydroxide
One kind；The quality for adding highly basic is 1-5 times, preferably twice of barium nitrate quality.
According to the present invention, described order mesoporous barium hydroxide catalyst is condensed in catalyzing iso-butane aldehyde and prepares 2,2,4- front threes
Application in base -1,3- pentanediol mono isobutyrates.
According to the present invention, it can be interval that described 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates, which prepare reaction,
Reaction unit can also be fixed bed reactors.
According to the present invention, the reaction temperature be 0-100 DEG C, preferably 10~40 DEG C, reaction time 1-12h, preferably
For 4h；Described order mesoporous barium hydroxide catalyst amount be isobutylaldehyde quality 0.1-100%, preferably 0.5~2%.
Beneficial effects of the present invention：
Compared with traditional barium hydroxide catalyst, the compound with regular structure of the catalyst, specific surface area is high, and meso-hole structure is favourable
Spread in product so that the reaction time is short, and conversion ratio and selectivity are all higher.
Brief description of the drawings
Fig. 1 is order mesoporous barium hydroxide A TEM electron microscopic pictures.
Fig. 2 is order mesoporous barium hydroxide A N2 adsorption desorption curve.
Fig. 3 is the GC spectrograms of products obtained therefrom.
Fig. 4 is to investigate experiment in the fixed bed life-span of products obtained therefrom.
Embodiment：
Method provided by the invention is described in detail with reference to embodiment, but the invention is not limited in any way.
The preparation of the materials A of embodiment 1
Enter 1g cetyl trimethylammonium bromides and 30g water in flask, after stirring, be added dropwise to mass fraction 5%
The aqueous solution 20g of barium nitrate, 45 DEG C are heated to, add the ammoniacal liquor stirring of 2g mass concentrations 28%, mixing time 6h.It is added dropwise to
10g mass fractions are 20% potassium hydroxide aqueous solution, are stirred vigorously 4h.Filtering, 72 are washed with ethanol using soxhlet extraction
Hour, both order mesoporous barium hydroxide A.
Pore-size distribution：10.7nm, pore volume 0.76cm3/g, specific surface area 442m2/g。
The material B of embodiment 2 preparation
Enter 2g Cetyltrimethylammonium bromides and 30g water in flask, after stirring, be added dropwise to mass fraction 10%
The aqueous solution 10g of barium nitrate, 55 DEG C are heated to, add the ammoniacal liquor stirring of 2g mass concentrations 28%, mixing time 8h.It is added dropwise to
10g mass fractions are 20% sodium hydrate aqueous solution, are stirred vigorously 8h.Filtering, 48 are washed with ethanol using soxhlet extraction
Hour, both order mesoporous barium hydroxide B.
The preparation of the material C of embodiment 3
Enter 2g hexadecyltrimethylammonium chlorides and 40g water in flask, after stirring, be added dropwise to mass fraction 5%
The aqueous solution 20g of barium nitrate, 30 DEG C are heated to, add the ammoniacal liquor stirring of 3g mass concentrations 28%, mixing time 6h.It is added dropwise to
10g mass fractions are 20% lithium hydroxide aqueous solution, are stirred vigorously 3h.Filtering, 36 are washed with ethanol using soxhlet extraction
Hour, both order mesoporous barium hydroxide C.
The material D of embodiment 4 preparation
Enter 2g OTACs and 10g water in flask, after stirring, be added dropwise to mass fraction 5%
The aqueous solution 20g of barium nitrate, 35 DEG C are heated to, add the ammoniacal liquor stirring of 5g mass concentrations 28%, mixing time 1h.It is added dropwise to
10g mass fractions are the 20% cesium hydroxide aqueous solution, are stirred vigorously 3h.Filtering, 48 are washed with ethanol using soxhlet extraction
Hour, both order mesoporous barium hydroxide D.
Embodiment 5：
The 5g catalyst A of synthesis is added in three-necked flask, 0 DEG C of maintenance reaction temperature, is slowly added dropwise in mixture of ice and water
Isobutylaldehyde 60g, 12h is reacted, after reaction terminates, the conversion ratio of isobutylaldehyde and 2,2,4- trimethyl -1,3- pentanediol list isobutyric acids
The selectivity of ester is analyzed with GC, and trimethyl -1, the 3- pentanediol mono isobutyrate of conversion ratio 87%, 2,2,4- is selectively
88%.
Embodiment 6：
The 2g catalyst B of synthesis is added in three-necked flask, maintenance reaction temperature 60 C, is slowly added dropwise isobutyl in a water bath
Aldehyde 100g, 4h is reacted, after reaction terminates, the conversion ratio of isobutylaldehyde and 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates
Selectivity is analyzed with GC, and trimethyl -1, the 3- pentanediol mono isobutyrate of conversion ratio 87%, 2,2,4- is selectively 88%.
Embodiment 7:
The 2g catalyst C of synthesis is added in three-necked flask, 40 DEG C of temperature is maintained in a water bath, isobutylaldehyde is slowly added dropwise
50g, 8h is reacted, after reaction terminates, the conversion ratio of isobutylaldehyde and 2, the selection of 2,4- trimethyl -1,3- pentanediol mono isobutyrates
Property analyzed with GC, conversion ratio 90%, 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates selectively be 88%.
Embodiment 8:
The 2g catalyst D of synthesis is filled into fixed bed, the isobutylaldehyde liquid of preheating, fixed bed reaction temperature are squeezed into pump
30 DEG C, flow velocity 10g/h of degree, takes the method for continuous sampling to evaluate the activity of catalyst, takes a sample to enter per hour
Row GC is analyzed, as a result as shown in figure 4, the conversion ratio of isobutylaldehyde is more than 90%, 2,2,4- trimethyl -1,3- pentanediol list isobutyls
The selectivity of acid esters selectivity maintains more than 85%, and catalyst activity maintains 48h non-inactivations.
The order mesoporous solid barium hydroxide catalyst efficiently isobutylaldehyde condensation can prepare 2,2,4- trimethyls -1,3- penta
Monoisobutyrate, the conversion ratio of isobutylaldehyde and 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates selectivity are reachable
More than 85%.Compared with traditional barium hydroxide catalyst, the ratio surface of the catalyst is high, and usage amount is low, good hydrothermal stability,
The service life length of catalyst.
Claims (10)
- A kind of 1. order mesoporous barium hydroxide catalyst, it is characterised in that：In the aqueous solution, in the presence of surfactant, Using barium nitrate as barium source, successively by weak base, highly basic two-step hydrolysis, the structure of order mesoporous barium hydroxide is formed.
- 2. according to the catalyst described in claim 1, it is characterised in that can prepare in accordance with the following steps：Enter surfactant and water in reaction vessel, after stirring, be added dropwise to the aqueous solution of barium nitrate, be heated to 30-60 DEG C, preferably 35 DEG C, add ammoniacal liquor stirring, preferably mixing time 1-12h, 6h；The aqueous solution of highly basic is added dropwise to, is acutely stirred Mix 1-12h, preferably 6h；Filtering, soxhlet extraction utilize with ethanol, washing 24-72h, both order mesoporous barium hydroxide.
- 3. according to the catalyst described in claim 1 or 2, it is characterised in that：Surfactant is cetyl trimethyl bromination Ammonium, hexadecyltrimethylammonium chloride, OTAC, one kind or two in Cetyltrimethylammonium bromide More than kind.
- 4. according to the catalyst described in claim 1, it is characterised in that：The mass ratio of surfactant and water is 1: 3-1: 50, Preferably 1：20；The mass fraction of barium nitrate is 1-20% in the aqueous solution of described barium nitrate.
- 5. according to the catalyst described in claim 1, it is characterised in that：Weak base is ammoniacal liquor, the mass concentration 25%- of ammoniacal liquor 28%, the quality for adding ammoniacal liquor is 1-5 times, preferably 5 times of barium nitrate quality.
- 6. according to the catalyst described in claim 1, it is characterised in that：The highly basic of addition can be sodium hydroxide, potassium hydroxide, Cesium hydroxide, a kind of reaction vessel in lithium hydroxide；The quality for adding highly basic is 1-5 times of barium nitrate quality, preferably two Times.
- 7. according to the catalyst described in claim 1, it is characterised in that：Order mesoporous barium hydroxide for long strip type cavernous structure Pore-size distribution 2-30nm, pore volume 0.05-1cm/g, specific surface area 10-800m2/g。
- 8. a kind of any described order mesoporous barium hydroxide catalyst of claim 1-7 prepares 2,2 in the condensation of catalyzing iso-butane aldehyde, Application in 4- trimethyl -1,3- pentanediol mono isobutyrates.
- 9. according to the application described in claim 8, it is characterised in that：Described 2,2,4- trimethyl -1,3- pentanediol list isobutyls Acid esters, which prepares reaction, can be carried out in intermittent reaction device or can also be carried out in fixed bed reactors.
- 10. according to the application described in claim 8, it is characterised in that：Reaction temperature be 0-100 DEG C, preferably 10~40 DEG C, instead It is 1-12h, preferably 4h between seasonable；Described order mesoporous barium hydroxide catalyst amount is the 0.1- of isobutylaldehyde quality 100%, preferably 0.5~2%.
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| CN1202873A (en) * | 1995-11-27 | 1998-12-23 | 工程吸气公司 | Process for producing calcium oxide, strontium oxide and barium oxide showing a high value of water sorption speed and oxides thus obtained |
| JP3557867B2 (en) * | 1997-09-18 | 2004-08-25 | 三菱マテリアル株式会社 | Method for producing low α-ray barium hydroxide and barium carbonate |
| CN101774619A (en) * | 2009-07-28 | 2010-07-14 | 贵州红星发展股份有限公司 | Method for preparing Ba(OH)2.8H2O |
| CN102688780A (en) * | 2012-06-04 | 2012-09-26 | 昆明理工大学 | Method for preparing organic and inorganic composite mesoporous solid base catalyst |
| WO2014096870A1 (en) * | 2012-12-21 | 2014-06-26 | Plaxica Limited | Process for producing lactic acid |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202873A (en) * | 1995-11-27 | 1998-12-23 | 工程吸气公司 | Process for producing calcium oxide, strontium oxide and barium oxide showing a high value of water sorption speed and oxides thus obtained |
| JP3557867B2 (en) * | 1997-09-18 | 2004-08-25 | 三菱マテリアル株式会社 | Method for producing low α-ray barium hydroxide and barium carbonate |
| CN101774619A (en) * | 2009-07-28 | 2010-07-14 | 贵州红星发展股份有限公司 | Method for preparing Ba(OH)2.8H2O |
| CN102688780A (en) * | 2012-06-04 | 2012-09-26 | 昆明理工大学 | Method for preparing organic and inorganic composite mesoporous solid base catalyst |
| WO2014096870A1 (en) * | 2012-12-21 | 2014-06-26 | Plaxica Limited | Process for producing lactic acid |
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