CN107824175A - For synthesizing loaded catalyst and its application of the hydroxy propanal of 2,2 dimethyl 3 - Google Patents
For synthesizing loaded catalyst and its application of the hydroxy propanal of 2,2 dimethyl 3 Download PDFInfo
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- CN107824175A CN107824175A CN201711054541.2A CN201711054541A CN107824175A CN 107824175 A CN107824175 A CN 107824175A CN 201711054541 A CN201711054541 A CN 201711054541A CN 107824175 A CN107824175 A CN 107824175A
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- alkali metal
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- isobutylaldehyde
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- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 title abstract 4
- BSABBBMNWQWLLU-UHFFFAOYSA-N lactaldehyde Chemical compound CC(O)C=O BSABBBMNWQWLLU-UHFFFAOYSA-N 0.000 title abstract 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 31
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 25
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 25
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 33
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000013618 particulate matter Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- JJMOMMLADQPZNY-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanal Chemical compound OCC(C)(C)C=O JJMOMMLADQPZNY-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011324 bead Substances 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000001354 calcination Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 101150116295 CAT2 gene Proteins 0.000 description 2
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 2
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 2
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 2
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 2
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HNBFUFIYQWYCDM-UHFFFAOYSA-N oxygen(2-) sulfane titanium(4+) Chemical compound [O--].[O--].S.[Ti+4] HNBFUFIYQWYCDM-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
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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
- 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
- B01J23/04—Alkali metals
-
- 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
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
-
- 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
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Loaded catalyst of the one kind for synthesizing the hydroxy propanal of 2,2 dimethyl 3, its feature, including:Active component and carrier, the active component are the one or more in the hydroxide, carbonate and fluoride of alkali metal, and the carrier is γ Al2O3;On the basis of the quality of carrier, the load capacity of active component is the 0.5~20% of vehicle weight.The present invention is using the formaldehyde and isobutylaldehyde of certain mol proportion as raw material, and apply described for synthesizing 2, the loaded catalyst of the hydroxy propanal of 2 dimethyl 3, is reacted using serialization method, is had simple to operate, reaction condition is gentle, reaction temperature is low, save energy consumption, conversion ratio and selectivity it is controllable the advantages that, it disclosure satisfy that isobutylaldehyde and formaldehyde prepare the requirement for the realization of industrialization for synthesizing the hydroxy propanal of 2,2 dimethyl 3.
Description
Technical field
It is used for the loaded catalyst and preparation method for synthesizing 2,2- pentaldols the present invention relates to one kind,
And the preparation technology of synthesis pentaldol.
Background technology
2,2- pentaldols (abbreviation HPA) are a kind of important organic compounds, are that vitamin medicaments are general
The intermediate of sour calcium, and the intermediate of important industrial chemicals neopentyl glycol.Neopentyl glycol is a kind of important fine chemistry industry
Product, it is widely used in producing various types of resins, plasticizer, synthetic lubricant fluid and surfactant etc..At present, both at home and abroad for 2,
The preparation of 2- pentaldols is mainly made using formaldehyde and isobutylaldehyde under conditions of catalyst.
As CN101863747B discloses the method that one kind prepares 2,2- pentaldols, the base catalysis
Agent selection is trimethylamine or triethylamine.CN105085212A discloses the method that one kind prepares 2,2- pentaldols,
The catalyst and carbonate and organic amine containing alkali metal, carbonate such as sodium carbonate, potassium carbonate etc. of alkali metal;Organic amine
Such as at least one of trimethylamine, triethylamine, triethanolamine and triisopropanolamine.Wherein inorganic base (Na2CO3、K2CO3、
NaHCO3) catalysis when dosage it is few, reaction temperature is relatively low, and selectivity is high, but has that conversion ratio is low, and side reaction is more, and easily corrosion is set
The shortcomings of standby and generation sodium formate etc. is not easy to remove in reaction system;Use organic amine (dimethylamine, triethylamine, trimethylamine etc.)
Reaction system is stable during catalysis, side reaction is few, high conversion rate, is the catalyst that overseas enterprise mainly uses at this stage, but also deposit
Selectivity not as good as inorganic base the shortcomings that.The preparation process for using anion exchange resin to make catalyst is also proposed, though product
It can be easily separated, but activity cycle is low, and catalytic efficiency is not also high.
CN102153456B discloses the method that one kind prepares 2,2- pentaldols, and the catalyst is 1,
8- diazabicylos [5,4,0] hendecene -7;10- methyl isophthalic acids, 8- diazabicylos [5,4,0] hendecene -7;Or 9- methyl isophthalic acids,
One kind in the alkene -6 of 7- diazabicylos [4,4,0] ten.Although such a catalyst activity is higher, it is easily recycled, system is present
It is standby difficult, the shortcomings of cost price costliness.
WO1997035825A1 does the condensation reaction of catalyst isobutylaldehyde and formaldehyde using MgO, but conversion ratio and
Selectivity is all relatively low.
CN101219939 uses a kind of alkali ionic liquid as aldol condensation catalyst, the ionic-liquid catalyst
Cation is 1,3- dialkylimidazolium cations, and anion is one kind in hydroxyl, carbonate, bicarbonate radical or acetate.
Although this method has the features such as corrosivity is small, and reactivity worth is good, and post catalyst reaction is easily isolated, is reusable,
It is set to be restricted in the big industrial applications of consumption because ionic liquid preparation cost is very expensive.
The content of the invention
The technical problems to be solved by the invention are the catalyst for synthesizing of HPA in the prior art, and its conversion ratio is low, secondary anti-
Although answer few more or side reaction, high conversion rate but selectivity low, or cost price is expensive, catalytic efficiency is not high, is unsuitable for
The problem of industrial applications etc..The present invention proposes a kind of loaded catalyst for being used to prepare 2,2- pentaldols,
Using the process of the catalyst isobutylaldehyde and formaldehyde synthesis 2,2- pentaldols, have that reaction temperature is low, bar
Part is gentle, saves energy consumption, the advantages that conversion ratio and selectivity are controllable.
In order to solve the above technical problems, technical scheme is as follows:
One kind is used for the loaded catalyst for synthesizing 2,2- pentaldols, and it includes active component and carrier,
The active component is the hydroxide of alkali metal, the one or more in carbonate and fluoride, the carrier be γ-
Al2O3;On the basis of the quality of carrier, the load capacity of active component is the 0.5~20% of carrier quality.Wherein, crystal formation is γ types
Aluminum oxide be γ-Al2O3, molecular weight 101.95.γ type aluminum oxide indissolubles or not soluble in water, it is a kind of porous material,
Every gram of internal surface area is up to hundreds of square metres, and active high absorption capacity is strong.Industrial goods are often colourless or pink micro-strip ball
Shape or cylindrical type particle, resistance to pressure are good.
Wherein, the hydroxide of the alkali metal refers to NaOH or KOH, and the carbonate of the alkali metal refers to Na2CO3Or
K2CO3, the fluoride of the alkali metal refers to NaF or KF.
Wherein, described γ-Al2O3Carrier refers to γ-Al2O3Bead, 1~5mm of particle diameter, 200~600m of specific surface area2/
g;Or γ-Al2O3Cylinder, 1~5mm of diameter, long 1~10mm, 200~600m of specific surface area2/g。
A kind of above-mentioned preparation method for being used to synthesize the loaded catalyst of 2,2- pentaldols, it includes
Following steps:
Step S1:One or more in the hydroxide, carbonate, fluoride of alkali metal are made into certain density water
Solution;
Step S2:The aqueous solution that step S1 is prepared is added drop-wise to carrier γ-Al at a certain temperature2O3On, and carry out homogeneous
Change operation, obtain being adsorbed with the γ-Al of one or more aqueous solution in the hydroxide of alkali metal, carbonate, fluoride2O3
Solid particulate matter;
Step S3:Under drying temperature, γ-Al that baking step S2 is obtained2O3Solid particulate matter;
Step S4:Then to the γ-Al of the obtained drying of step S32O3Solid particulate matter, raised with certain heating rate
To under a sintering temperature, roasting a period of time, then cool, obtain described for synthesizing 2,2- dimethyl -3- hydroxyls
The loaded catalyst of propionic aldehyde.
Wherein, it is preferred that the hydroxide of the alkali metal described in step S1, carbonate, one kind in fluoride or more
Kind refers to NaOH, Na2CO3、KOH、K2CO3, one or more in KF, NaF.
Wherein, it is preferred that the carrier γ-Al described in step S22O3Refer to γ-Al2O3Bead, 1~5mm of particle diameter, compare table
200~600m of area2/g;Or γ-Al2O3Cylinder, 1~5mm of diameter, long 1~10mm, 200~600m of specific surface area2/g。
Wherein, it is preferred that in step S1 by one kind in the hydroxide, carbonate, fluoride of described alkali metal or
The concentration of a variety of aqueous solution being configured to is mass fraction 1~30%, preferably 10~20%.
Wherein, it is preferred that to carrier γ-Al in the step S22O3The operating environment temperature range that the aqueous solution is added dropwise is normal
Temperature~100 DEG C, preferably 50-80 DEG C.Because temperature can also influence carrier γ-Al2O3Absorption property and the catalyst finally obtained
Activity component load quantity, therefore be added dropwise the aqueous solution operating environment temperature be also an important parameter.
Wherein, it is preferred that in the step S2, the aqueous solution is being added dropwise to carrier γ-Al2O3During homogenize operation when
Long 0.5~2h.
Wherein, it is preferred that in the step S3, described drying temperature scope is 80~150 DEG C, preferably 100~120
℃。
Wherein, it is preferred that in the step S4, described heating rate scope is 1~20 DEG C/min, preferably 5~10 DEG C/
min。
Wherein, it is preferred that in the step S4, described sintering temperature scope is 300~700 DEG C, preferably 400~550
℃;It is calcined 1~8h of duration, preferably 2~4h.
The present invention also protection one kind is with the γ-Al2O3For carrier composite catalyst using formaldehyde and isobutylaldehyde as original
Material, catalyzes and synthesizes preparation 2, the application in 2- pentaldols (HPA).It is described with γ-Al2O3Compound for carrier is urged
Agent with the hydroxide, carbonate and fluoride of alkali metal one or more for active component, using the quality of carrier as
Benchmark, the load capacity of the active component are the 0.5~20% of vehicle weight.
The solution of the present invention also includes:The method that one kind prepares 2,2- pentaldols, methods described is with certain
The formaldehyde and isobutylaldehyde of mol ratio are raw material, it is characterized in that, the catalyst for reacting used be it is that any of the above scheme is described or
The loaded catalyst for being used to synthesize pentaldol obtained by preparation method.
Wherein, in the reaction, mol ratio, charging rate, temperature by controlling formaldehyde and isobutylaldehyde etc. controls raw material
The selectivity of reaction rate and product.
Wherein, the warm of a raw material is included:After formalin and isobutylaldehyde are distinguished into preheated processing,
Reacted simultaneously with the loaded catalyst contact for being used to synthesize 2,2- pentaldols again, synthesis 2,2-
Pentaldol.
Wherein, the reaction is carried out in fixed bed reactors, described to be used to synthesize 2,2- pentaldols
Loaded catalyst is piled into certain thickness bed.
Wherein, the mol ratio of the formaldehyde and isobutylaldehyde is (0.8~1.5):1.
Wherein, the mass space velocity of described isobutylaldehyde is 0.5~2.0h-1。
Described reaction temperature is room temperature~120 DEG C, preferably 70~100 DEG C.
Wherein, described fixed bed reactors, also known as packed bed reactor, solid catalyst or solid reactant are filled with
To realize a kind of reactor of heterogeneous reaction process.Solids is generally in granular form, and is piled into certain thickness bed.Bed
Transfixion, fluid are reacted by bed.It is with fluidized-bed reactor and the difference of moving-burden bed reactor is solid
Grain remains static.Fixed bed reactors are typically mainly used in realizing the catalytic reaction of gas-solid phase, such as ammonia convertor, titanium dioxide
Sulphur contact oxidation device, hydrocarbon steam converting furnace etc..
The present invention has the following technical effect that:
γ-Al of the present invention2O3One or more in the hydroxide of the alkali metal of load, carbonate and fluoride is urge
Agent, using the formaldehyde of certain mol proportion and isobutylaldehyde as raw material, reacted using serialization method, there is simple to operate, reaction
Mild condition, reaction temperature is low, save energy consumption, conversion ratio and selectivity it is controllable the advantages that, disclosure satisfy that isobutylaldehyde and formaldehyde
Prepare the requirement of the realization of industrialization of synthesis pentaldol.The pentaldol of the present invention
Preparation method, this method have it is selectively high to HPA the advantages of.It is different when synthesis reaction temperature is 80 DEG C according to experimental verification
Butyraldehyde conversion ratio reaches 99.7%, selectivity up to 99.2%.
Wherein, in carrier γ-Al2O3After adsorption activity component, again using the form of high-temperature roasting, it is further able to ensure
The activity and stability of catalyst.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the several of the present invention
Technical scheme in the embodiment of the present invention is clearly and completely described specific embodiment, it is clear that described embodiment is
Part of the embodiment of the present invention, rather than whole embodiments.
The loaded catalyst of 2,2- pentaldols is combined to suitable for industry the invention discloses one kind, its
Including active component and carrier, the active component is hydroxide, carbonate and one kind or more in fluoride of alkali metal
Kind, the carrier is γ-Al2O3;On the basis of the quality of carrier, the load capacity of active component for vehicle weight 0.5~
20%.The hydroxide of described alkali metal, carbonate, the one or more in fluoride, in particular to NaOH, Na2CO3、
KOH、K2CO3, one or more in KF, NaF.
Invention additionally discloses the preparation method of the loaded catalyst of synthesis 2, the 2- pentaldols, bag
Include:
Step S1:One or more in the hydroxide, carbonate, fluoride of alkali metal are made into certain density water
Solution;One or more in the hydroxide of alkali metal described in step S1, carbonate, fluoride refer to NaOH,
Na2CO3、KOH、K2CO3, one or more in KF, NaF, the concentration of the aqueous solution is mass fraction 1~30%, preferably 10~
20%.
Step S2:The aqueous solution that step S1 is prepared is added drop-wise to carrier γ-Al at a certain temperature2O3On, and carry out homogeneous
Change operation, obtain being adsorbed with the γ-Al of one or more aqueous solution in the hydroxide of alkali metal, carbonate, fluoride2O3
Solid particulate matter;Carrier γ-Al2O3Refer to γ-Al2O3Bead, 1~5mm of particle diameter, 200~600m of specific surface area2/g;Or γ-
Al2O3Cylinder, 1~5mm of diameter, long 1~10mm, 200~600m of specific surface area2/g.The operating environment temperature model of the aqueous solution is added dropwise
It is normal temperature~100 DEG C to enclose, preferably 50-80 DEG C.Homogenize operation 0.5~2h of duration, including the operation such as stirs, shakes.
Step S3:Under drying temperature, γ-Al that baking step S2 is obtained2O3Solid particulate matter;Drying temperature scope is
80~150 DEG C, preferably 100~120 DEG C.
Step S4:Then to the γ-Al of the obtained drying of step S32O3Solid particulate matter is raised with certain heating rate
To under a sintering temperature, roasting a period of time, then cool, obtain described for synthesizing 2,2- dimethyl -3- hydroxyls
The loaded catalyst of propionic aldehyde.Heating rate scope is 1~20 DEG C/min, preferably 5~10 DEG C/min.Sintering temperature scope is
300~700 DEG C, preferably 400~550 DEG C;It is calcined 1~8h of duration, preferably 2~4h.
The present invention also protect it is a kind of it is described synthesis pentaldol loaded catalyst with formaldehyde with
Isobutylaldehyde is raw material, catalyzes and synthesizes preparation 2, the application in 2- pentaldols (HPA).
Present invention additionally comprises the loaded catalyst of application synthesis 2, the 2- pentaldols, necessarily to rub
The formaldehyde and isobutylaldehyde of your ratio are raw material, the method for preparing synthesis 2,2- pentaldols.
Specifically, the synthesis 2 that will be prepared, the loaded catalyst of 2- pentaldols is in fixed bed reaction
In device, certain thickness bed is piled into, formalin and isobutylaldehyde are squeezed into preheater by feed pump respectively, is preheated
Raw material afterwards, which enters in fixed bed reactors, to be reacted, by the mol ratio, charging rate, temperature that control formaldehyde and isobutylaldehyde
Etc. controlling the selectivity of raw material reaction rate and product.
To help to understand, the loaded catalyst of 2,2- pentaldols is synthesized to the present invention individually below
Preparation method and application are illustrated:
Embodiment 1:Catalyst Cat-1 preparation
The use of grain diameter 2-3mm, specific surface area is about 350-400m2/ g γ-Al2O3Bead 100g is carrier, is prepared
The KOH aqueous solution of mass fraction 1%, the aqueous solution is added drop-wise to γ-Al at 90 DEG C2O3On carrier, when stirring shared in absorption
1h.The volume of solution used is 70mL.Then γ-the Al of the KOH aqueous solution will be adsorbed2O3Particulate matter mistake in baking oven at 120 DEG C
Night, drying.Then by dry γ-Al2O3For particulate matter in Muffle kiln roasting, calcination procedure is that room temperature starts with 5 DEG C/min's
Programming rate is warming up to 300 DEG C, is then incubated 4h, after be cooled to room temperature, obtain γ-Al2O3Loaded catalyst, it is standby;And mark
It is designated as Cat-1, load capacity 0.7%,.
Embodiment 2:Catalyst Cat-2 preparation
The use of grain diameter 3-4mm, specific surface area is about 550-600m2/ g γ-Al2O3Bead 100g is carrier.Prepare
The Na of mass fraction 30%2CO3The aqueous solution, the aqueous solution is added drop-wise to γ-Al at 40 DEG C2O3On carrier, stirred altogether in absorption
Used time 2h, the volume of solution used is 65mL.Then Na will be adsorbed2CO3γ-the Al of the aqueous solution2O3Particulate matter is at 100 DEG C
In baking oven overnight, to drying.Then by the γ-Al after drying2O3Particulate matter is opened in Muffle kiln roasting, calcination procedure for room temperature
Begin with 10 DEG C/min programming rate to be warming up to 700 DEG C, be then incubated 6h, after cool, obtain γ-Al2O3Supported catalyst
Agent, it is standby;And it is labeled as Cat-2, load capacity 19.5%.
Embodiment 3:Catalyst Cat-3 preparation
Use grain diameter 2-4mm, 500~600m of specific surface area2/ g γ-Al2O3Bead 100g is carrier.Prepare matter
The KF aqueous solution of fraction 15% is measured, the aqueous solution is added drop-wise to γ-Al at 30 DEG C2O3On carrier, stirred in absorption, when sharing
0.5h.The volume of solution used is 60mL.Then γ-the Al of the KF aqueous solution will be adsorbed2O3Particulate matter mistake in baking oven at 80 DEG C
Night.Then by the γ-Al after drying2O3For particulate matter in Muffle kiln roasting, calcination procedure is that room temperature starts with 2 DEG C/min liter
Warm speed is warming up to 500 DEG C, is then incubated 4h, after cool, it is standby.Labeled as Cat-3, load capacity 9%.
Embodiment 4:Catalyst Cat-4 preparation
Use 100g γ-Al2O3Cylinder is carrier, a diameter of 1.5mm, length 1-3mm, 200~300m of specific surface area2/g。
The NaOH aqueous solution of mass fraction 20% is prepared, the aqueous solution is added drop-wise to γ-Al at 80 DEG C2O3On carrier, stirred in absorption
Mix, 0.5h when sharing.The volume of solution used is 45mL.Then γ-the Al of the NaOH aqueous solution will be adsorbed2O3Particulate matter is 80
At DEG C in baking oven overnight.Then by the γ-Al after drying2O3Particulate matter in Muffle kiln roasting, calcination procedure be room temperature start with
20 DEG C/min heating rate is warming up to 650 DEG C, is then incubated 8h, after cool, it is standby.Labeled as Cat-4, load capacity is
9%.
Embodiment 5:Catalyst Cat-5 preparation
Use 100g γ-Al2O3Cylinder is carrier, a diameter of 3mm, length 1-5mm, 500~600m of specific surface area2/g.Match somebody with somebody
The K of mass fraction 3% processed2CO3The aqueous solution, the aqueous solution is added drop-wise to γ-Al at 35 DEG C2O3On carrier, stirred altogether in absorption
Used time 2h.The volume of solution used is 90mL.Then K will be adsorbed2CO3γ-the Al of the aqueous solution2O3Particulate matter dries at 150 DEG C
In case overnight.Then by the γ-Al after drying2O3Particulate matter in Muffle kiln roasting, calcination procedure be room temperature start with 20 DEG C/
Min heating rate is warming up to 400 DEG C, is then incubated 6h, after cool, it is standby.Labeled as Cat-5, load capacity is
2.7%.
Embodiment 6:Catalyst Cat-6 preparation
Use 100g γ-Al2O3Cylinder is carrier, a diameter of 2mm, length 5-7mm, 400~450m of specific surface area2/g.Match somebody with somebody
The NaF aqueous solution of mass fraction 20% processed, the aqueous solution is added drop-wise to γ-Al at 50 DEG C2O3On carrier, stirred altogether in absorption
Used time 1h.The volume of solution used is 65mL.Then γ-the Al of the NaF aqueous solution will be adsorbed2O3Particulate matter baking oven at 140 DEG C
In overnight.Then by the γ-Al after drying2O3For particle in Muffle kiln roasting, calcination procedure is that room temperature starts with 10 DEG C/min's
Heating rate is warming up to 550 DEG C, is then incubated 2h, after cool, it is standby.Labeled as Cat-6, load capacity 13%.
The catalytic reaction process of embodiment 7
The catalyst of constant weight prepared in embodiment 1-6 is put in fixed bed reactors respectively and is piled into necessarily
The bed of thickness, reactor inside diameter 20mm, length 70cm.Formalin and isobutylaldehyde using 37% are raw material, and raw material passes through
It is passed through fixed bed reactors simultaneously after preheating and is contacted with catalyst and reacts.It is as shown in the table, control formaldehyde and isobutylaldehyde
Mol ratio, charging rate, reaction temperature etc. control the selectivity of raw material reaction rate and product.It is reacted, obtain product
Pentaldol.Product is analyzed using gas-chromatography after reaction, using area normalization method, except formaldehyde
Outside calculated by peak area caused by all material be 100%.
The area percentage of the conversion ratio of isobutylaldehyde=100%- isobutylaldehydes
Area/isobutylaldehyde of selectivity=pentaldol of pentaldol turns
Rate × 100.
Wherein when from the catalyst Cat-3 of embodiment 3, dosage 30g, the charging rate of formalin is 0.50ml/
Min, the charging rate 0.469ml/min of isobutylaldehyde, formaldehyde and isobutylaldehyde mol ratio=1.2:1, during 80 DEG C of reaction temperature, use
Gas-chromatography is analyzed, and the conversion ratio of isobutylaldehyde reaches 99.7%, and the selectivity of 2,2- pentaldols is up to
99.2%.
Above specific experiment proves, the use of alkali metal hydroxide of the present invention, carbonate or fluoride is active component
γ-Al2O3Loaded catalyst, makes the reaction of formaldehyde and synthetically prepared 2, the 2- pentaldols of isobutylaldehyde have operation
Simply, mild condition, temperature is low, save energy consumption, conversion ratio and selectivity it is very high the advantages that, disclosure satisfy that isobutylaldehyde and formaldehyde
Prepare the requirement of the realization of industrialization of synthesis pentaldol.
It the above is only the scope that claimed invention is not intended to limit to the detailed description of embodiments of the invention,
But it is merely representative of the selected embodiment of the present invention.Based on the embodiment in the present invention, those of ordinary skill in the art are not having
The every other embodiment obtained under the premise of creative work is made, belongs to the scope of protection of the invention.
Claims (15)
1. loaded catalyst of the one kind for synthesizing 2,2- pentaldols, its feature, including:Active component and
Carrier, the active component are the one or more in the hydroxide, carbonate and fluoride of alkali metal, and the carrier is
γ-Al2O3;On the basis of the quality of carrier, the load capacity of active component is the 0.5~20% of vehicle weight.
2. loaded catalyst according to claim 1, it is characterised in that the hydroxide of the alkali metal refers to NaOH
Or KOH, the carbonate of the alkali metal refer to Na2CO3Or K2CO3, the fluoride of the alkali metal refers to NaF or KF.
3. loaded catalyst according to claim 1 or 2, it is characterised in that described γ-Al2O3Carrier refer to γ-
Al2O3Bead, 1~5mm of particle diameter, 200~600m of specific surface area2/g;Or γ-Al2O3Cylinder, 1~5mm of diameter, long 1~10mm,
200~600m of specific surface area2/g。
4. a kind of prepare is urged as described in claim any one of 1-3 for synthesizing the support type of pentaldol
The method of agent, it comprises the following steps:
Step S1:One or more in the hydroxide, carbonate, fluoride of alkali metal are made into certain density water-soluble
Liquid;
Step S2:The aqueous solution that step S1 is prepared is added drop-wise to carrier γ-Al at a certain temperature2O3On, and carry out the behaviour that homogenizes
Make, obtain being adsorbed with the γ-Al of one or more aqueous solution in the hydroxide of alkali metal, carbonate, fluoride2O3Solid
Particulate matter;
Step S3:Under drying temperature, γ-Al that baking step S2 is obtained2O3Solid particulate matter;
Step S4:Then to the γ-Al of the obtained drying of step S32O3Solid particulate matter, one is increased to certain heating rate
Under individual sintering temperature, roasting a period of time, then cool, obtain described for synthesizing 2,2- pentaldols
Loaded catalyst.
5. according to the method for claim 4, it is characterised in that by the hydroxide of described alkali metal, carbon in step S1
The concentration for the aqueous solution that one or more in hydrochlorate, fluoride are configured to is mass fraction 1~30%, preferably 10~20%.
6. according to the method for claim 4, it is characterised in that to carrier γ-Al in the step S22O3The aqueous solution is added dropwise
Operating environment temperature range be normal temperature~100 DEG C, preferably 50-80 DEG C.
7. according to the method for claim 4, it is characterised in that in the step S3, described drying temperature scope is 80
~150 DEG C, preferably 100~120 DEG C.
8. according to the method for claim 4, it is characterised in that in the step S4, described heating rate scope is 1~
20 DEG C/min, preferably 5~10 DEG C/min.
9. according to the method for claim 4, it is characterised in that in the step S4, described sintering temperature scope is 300
~700 DEG C, preferably 400~550 DEG C;It is calcined 1~8h of duration, preferably 2~4h.
10. the method that one kind prepares 2,2- pentaldols, using the formaldehyde of certain mol proportion and isobutylaldehyde as raw material,
Characterized in that, the used catalyst of reaction is that loaded catalyst according to claim any one of 1-3 or right will
The catalyst for asking the method described in any one of 4-11 to be prepared.
11. according to the method for claim 10, it is characterised in that also include the warm of a raw material:I.e. by formaldehyde
After the aqueous solution and isobutylaldehyde distinguish preheated processing, then it is used to synthesize the negative of 2,2- pentaldols with described simultaneously
Supported catalyst contact is reacted, and synthesizes 2,2- pentaldols.
12. according to the method for claim 11, it is characterised in that the reaction is carried out in fixed bed reactors, described
Loaded catalyst for synthesizing pentaldol is piled into certain thickness bed.
13. according to the method for claim 10, it is characterised in that the mol ratio of the formaldehyde and isobutylaldehyde for (0.8~
1.5):1.
14. according to the method for claim 13, it is characterised in that the mass space velocity of described isobutylaldehyde is 0.5~2.0h-1。
15. according to the method for claim 10, it is characterised in that described reaction temperature is room temperature~120 DEG C, preferably 70
~100 DEG C.
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