CN107662937B - A kind of order mesoporous barium hydroxide catalyst and its application in the preparation of 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate - Google Patents
A kind of order mesoporous barium hydroxide catalyst and its application in the preparation of 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate Download PDFInfo
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- CN107662937B CN107662937B CN201610621929.5A CN201610621929A CN107662937B CN 107662937 B CN107662937 B CN 107662937B CN 201610621929 A CN201610621929 A CN 201610621929A CN 107662937 B CN107662937 B CN 107662937B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 title claims abstract description 35
- 229910001863 barium hydroxide Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 title abstract description 8
- 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 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 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 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 239000000908 ammonium hydroxide Substances 0.000 claims description 12
- 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
- 235000019441 ethanol Nutrition 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000944 Soxhlet extraction Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 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 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- -1 iso-butane aldehyde Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-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
- 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
- NNPPMTNAJDCUHE-UHFFFAOYSA-N trimethylmethane Natural products CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- 229910052792 caesium Inorganic materials 0.000 claims 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 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
- 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 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 239000002585 base Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 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
- 239000000203 mixture Substances 0.000 description 2
- 230000001376 precipitating effect 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate.The catalyst is using barium nitrate as barium source, after weak base prehydrolysis, under the action of surfactant, forms meso-hole structure and finally in the presence of a strong base forms the structure of order mesoporous barium hydroxide.The order mesoporous solid barium hydroxide catalyst can efficiently 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates of isobutylaldehyde condensation preparation, the conversion ratio of isobutylaldehyde and 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate selectivity be equal up to 85% or more.Compared with traditional barium hydroxide catalyst, the specific surface of the catalyst is high, and usage amount is low, good hydrothermal stability, the long service life 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 isobutyrate.
Background technique
2,2,4- trimethyl -1,3- pentanediol mono isobutyrates, also known as alcohol ester 12 are a kind of higher boilings, 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 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 product using more and more extensive.
1,3- glycol and such as 2,2,4- trimethyl -1,3- pentanediol list isobutyl of their monoesters product are prepared from corresponding aldehyde
Acid esters has 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 adds hydrogen 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 under the effect of the catalyst, isobutylaldehyde is condensed first as 2,2,4- trimethyl -1,
3- pentanediol mono isobutyrate, then further react to obtain product with isobutylaldehyde.The investment of this method simple process is small, but exists
The more problem of side reaction.It is mainly at present base catalyst about the catalyst of direct synthesis technique.Such as patent CN 1417195A
In disclose it is a kind of using barium hydroxide be catalyst synthetic method.A kind of utilization is disclosed in 101863762 A of patent CN
Stratiform magnalium anionic clay is the method that the two-step method of catalyst prepares alcohol ester 12.
But catalyst used so far is all commercialized barium hydroxide, specific surface area is small, and structure is irregular,
The component that catalytic action can be played is few, therefore the quality of the required catalyst of its in reaction process is more, and the time is long.And utilize barium
It is fast that salt precipitating prepares the method for barium hydroxide its settling velocity, it is more difficult to form orderly meso-hole structure.Therefore develop new method
Preparing order mesoporous barium hydroxide becomes challenge.
Summary 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 precipitating, enables barium salt prehydrolysis first and under the action of surfactant, is formed orderly
Meso-hole structure, and finally obtain order mesoporous barium hydroxide.Under the catalyst action, the conversion ratio of isobutylaldehyde and 2,2,4- tri-
Methyl-1,3- pentanediol mono isobutyrate selectivity is up to 90% or more.
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, which can be prepared as follows:
Enter surfactant and water in flask, after mixing evenly, is added dropwise to the aqueous solution of barium nitrate, is heated to 30-60
DEG C, preferably 35 DEG C, ammonium hydroxide stirring, mixing time 1-12h, preferably 6h is added.It is added dropwise to the aqueous solution of highly basic, is acutely stirred
Mix 1-12h, preferably 6h.Filtering, with ethyl alcohol utilize soxhlet extraction, wash 24-72 hours, both order mesoporous hydroxide
Barium.
According to the present invention, the surfactant be cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride,
Octadecyltrimethylammonium chloride, one of 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 that ammonium hydroxide is added 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 that highly basic is added is 1-5 times, preferably twice of barium nitrate quality.
According to the present invention, the order mesoporous barium hydroxide catalyst is condensed 2,2,4- front threes of preparation in catalyzing iso-butane aldehyde
Application in base -1,3- pentanediol mono isobutyrate.
According to the present invention, the preparation reaction of described 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates can be interval
Reaction unit is also possible to 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；The 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 advantageous
It is spread in product, so that the reaction time is short, conversion ratio and selectivity are all higher.
Detailed description of the invention
Fig. 1 is the TEM electron microscopic picture of order mesoporous barium hydroxide A.
Fig. 2 is the N2 adsorption desorption curve of order mesoporous barium hydroxide A.
Fig. 3 is the GC spectrogram of products obtained therefrom.
Fig. 4 is to investigate experiment in the fixed bed service life of products obtained therefrom.
Specific embodiment:
Method provided by the invention is described in detail below with reference to embodiment, but the invention is not limited in any way.
The preparation of 1 materials A of embodiment
Enter 1g cetyl trimethylammonium bromide and 30g water in flask, after mixing evenly, is added dropwise to mass fraction 5%
The aqueous solution 20g of barium nitrate is heated to 45 DEG C, and the stirring of 28% ammonium hydroxide of 2g mass concentration, mixing time 6h is added.It is added dropwise to
The potassium hydroxide aqueous solution that 10g mass fraction is 20%, is vigorously stirred 4h.Filtering washs 72 using soxhlet extraction with ethyl alcohol
Hour, both order mesoporous barium hydroxide A.
Pore-size distribution: 10.7nm, Kong Rong 0.76cm3/g, specific surface area 442m2/g。
The preparation of 2 material B of embodiment
Enter 2g Cetyltrimethylammonium bromide and 30g water in flask, after mixing evenly, is added dropwise to mass fraction 10%
The aqueous solution 10g of barium nitrate is heated to 55 DEG C, and the stirring of 28% ammonium hydroxide of 2g mass concentration, mixing time 8h is added.It is added dropwise to
The sodium hydrate aqueous solution that 10g mass fraction is 20%, is vigorously stirred 8h.Filtering washs 48 using soxhlet extraction with ethyl alcohol
Hour, both order mesoporous barium hydroxide B.
The preparation of 3 material C of embodiment
Enter 2g hexadecyltrimethylammonium chloride and 40g water in flask, after mixing evenly, is added dropwise to mass fraction 5%
The aqueous solution 20g of barium nitrate is heated to 30 DEG C, and the stirring of 28% ammonium hydroxide of 3g mass concentration, mixing time 6h is added.It is added dropwise to
The lithium hydroxide aqueous solution that 10g mass fraction is 20%, is vigorously stirred 3h.Filtering washs 36 using soxhlet extraction with ethyl alcohol
Hour, both order mesoporous barium hydroxide C.
The preparation of 4 material D of embodiment
Enter 2g octadecyltrimethylammonium chloride and 10g water in flask, after mixing evenly, is added dropwise to mass fraction 5%
The aqueous solution 20g of barium nitrate is heated to 35 DEG C, and the stirring of 28% ammonium hydroxide of 5g mass concentration, mixing time 1h is added.It is added dropwise to
The cesium hydroxide aqueous solution that 10g mass fraction is 20%, is vigorously stirred 3h.Filtering washs 48 using soxhlet extraction with ethyl alcohol
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 maintaining reaction temperature, is slowly added dropwise in mixture of ice and water
Isobutylaldehyde 60g reacts 12h, after reaction, 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 87%, 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate of conversion ratio is selectively
88%.
Embodiment 6:
The 2g catalyst B of synthesis is added in three-necked flask, 60 DEG C of maintaining reaction temperature, are slowly added dropwise isobutyl in a water bath
Aldehyde 100g reacts 4h, after reaction, the conversion ratio of isobutylaldehyde and 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates
Selectivity is analyzed with GC, and 87%, 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate of conversion ratio 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 reacts 8h, after reaction, the conversion ratio of isobutylaldehyde and 2, the selection of 2,4- trimethyl -1,3- pentanediol mono isobutyrates
Property is analyzed with GC, and conversion ratio 90%, 2,2,4- trimethyl -1,3- pentanediol mono isobutyrates are selectively 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
Degree 30 DEG C, flow velocity 10g/h, take the method for continuous sampling to evaluate the activity of catalyst, take per hour a sample into
Row GC analysis, as a result as shown in figure 4, the conversion ratio of isobutylaldehyde is in 90% or more, 2,2,4- trimethyl -1,3- pentanediol list isobutyl
The selectivity of acid esters selectivity maintains 85% or more, and catalyst activity maintains 48h non-inactivation.
The order mesoporous solid barium hydroxide catalyst efficiently isobutylaldehyde condensation can prepare 2,2,4- trimethyl -1,3- penta
Monoisobutyrate, the conversion ratio of isobutylaldehyde and 2,2,4- trimethyl -1,3- pentanediol mono isobutyrate selectivity are reachable
85% or more.Compared with traditional barium hydroxide catalyst, the specific surface of the catalyst is high, and usage amount is low, good hydrothermal stability,
The long service life of catalyst.
Claims (15)
1. a kind of order mesoporous barium hydroxide catalyst, it is characterised in that: in aqueous solution, in the presence of surfactant,
Using barium nitrate as barium source, successively passes through weak base, highly basic two-step hydrolysis, form the structure of order mesoporous barium hydroxide.
2. catalyst described in accordance with the claim 1, which is characterized in that can prepare in accordance with the following steps:
Enter surfactant and water in the reaction vessel, after mixing evenly, is added dropwise to the aqueous solution of barium nitrate, is heated to 30-60
DEG C, ammonium hydroxide stirring, mixing time 1-12h is added；It is added dropwise to the aqueous solution of highly basic, is vigorously stirred 1-12h；Filtering, uses ethyl alcohol
Using soxhlet extraction, wash 24-72h, both order mesoporous barium hydroxide.
3. catalyst according to claim 2, which is characterized in that can prepare in accordance with the following steps: in the reaction vessel
Enter surfactant and water, after mixing evenly, be added dropwise to the aqueous solution of barium nitrate, be heated to 35 DEG C, ammonium hydroxide stirring, stirring is added
Time is 6h；It is added dropwise to the aqueous solution of highly basic, is vigorously stirred 6h；Filtering utilizes soxhlet extraction with ethyl alcohol, washs 24-72h,
Both order mesoporous barium hydroxide.
4. catalyst according to claim 1 or 2, it is characterised in that: surfactant is cetyl trimethyl bromination
Ammonium, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, one of Cetyltrimethylammonium bromide or two
Kind or more.
5. catalyst described in accordance with the claim 1, it is characterised in that: the mass ratio of surfactant and water is 1:3-1:50；
The mass fraction of barium nitrate is 1-20% in the aqueous solution of the barium nitrate.
6. catalyst according to claim 5, it is characterised in that: the mass ratio of surfactant and water is 1:20.
7. catalyst described in accordance with the claim 1, it is characterised in that: weak base is ammonium hydroxide, the mass concentration 25%- of ammonium hydroxide
28%, the quality that ammonium hydroxide is added is 1-5 times of barium nitrate quality.
8. catalyst according to claim 7, it is characterised in that: the quality that ammonium hydroxide is added is 5 times of barium nitrate quality.
9. catalyst described in accordance with the claim 1, it is characterised in that: the highly basic of addition is sodium hydroxide, potassium hydroxide, hydrogen-oxygen
Change caesium, one or more of lithium hydroxide；The quality that highly basic is added is 1-5 times of barium nitrate quality.
10. catalyst according to claim 9, it is characterised in that: the quality that highly basic is added is twice of barium nitrate quality.
11. catalyst described in accordance with the claim 1, it is characterised in that: order mesoporous barium hydroxide is the poroid knot of long strip type
Structure pore-size distribution 2-30nm, Kong Rong 0.05-1cm/g, specific surface area 10-800m2/g。
12. a kind of any order mesoporous barium hydroxide catalyst of claim 1-11 prepares 2 in the condensation of catalyzing iso-butane aldehyde,
Application in 2,4- trimethyl -1,3- pentanediol mono isobutyrate.
13. applying according to claim 12, it is characterised in that: described 2,2,4- trimethyl -1,3- pentanediol Dan Yi
Butyrate preparation reaction, which can be, to be carried out or is also possible to carry out in fixed bed reactors in intermittent reaction device.
14. applying according to claim 12, it is characterised in that: reaction temperature is 0-100 DEG C, reaction time 1-12h；
The order mesoporous barium hydroxide catalyst amount is the 0.1-100% of isobutylaldehyde quality.
15. application according to claim 14, it is characterised in that: reaction temperature is 10~40 DEG C, reaction time 4h；Institute
The order mesoporous barium hydroxide catalyst amount stated is the 0.5~2% of isobutylaldehyde quality.
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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 |
-
2016
- 2016-07-29 CN CN201610621929.5A patent/CN107662937B/en active Active
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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