CN107051557A - A kind of barium pyrophosphate load cesium-promoted catalyst and preparation method thereof, application - Google Patents
A kind of barium pyrophosphate load cesium-promoted catalyst and preparation method thereof, application Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
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- 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
- C07C45/48—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation involving decarboxylation
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Abstract
The present invention provides a kind of barium pyrophosphate load cesium-promoted catalyst and preparation method thereof, application, it is that the barium pyrophosphate that the method calcined on barium nitrate, ammonium dihydrogen phosphate and cesium nitrate by two steps is synthesized loads cesium-promoted catalyst, and preparation method thereof and lactic acid be condensed prepare 2,3 pentanedione techniques in application.Take 15.68g barium nitrates to be dissolved in 300mL distilled water and be sufficiently stirred for 30min, then suction filtration after 6.34g diammonium hydrogen phosphate stirring reactions 2h is added into solution, precipitated 3 times with distillation water washing, be transferred in 120 DEG C of baking oven and dry 10h.Hereafter it is placed in Muffle furnace and is calcined 3h at 500 DEG C, obtains barium pyrophosphate carrier.Then, obtained barium pyrophosphate is prepared into barium pyrophosphate support type cesium catalyst as carrier using infusion process.Catalyst prepared by the inventive method continuously runs 28h, and the selectivity of catalyst is almost unchanged.Preparation method is simple, and environmental protection is with low cost, and catalytic activity is high, and stability is good.
Description
Technical field
The present invention relates to source chemical technology field, more particularly to a kind of barium pyrophosphate load cesium-promoted catalyst and its preparation side
Method, application.
Background technology
2,3- pentanediones are a kind of high value fine chemicals of purposes widely.Prepare the classics side of 2,3- pentanediones
Method mainly has 2 kinds：One is extracted from the essential oils such as Finland pine, but raw material sources are limited, production cost height and low yield.Two are
Under conditions of hydroxylamine hydrochloride is present and is protected with nitrogen, made with excessive natrium nitrosum and watery hydrochloric acid oxidation methyl propyl group ketone
Standby, the technique is using petroleum-based products as raw material, and cost is higher, and production process has the environmental issues such as spent acid yield is big.With stone
The continuous anxiety of oily resource is increasingly strict with environmental protection policy, and exploitation substitutes fossil feedstock with reproducible organism-based raw material and produced
Chemicals is received significant attention.The derivative of the typical biomass of lactic acid series, it is one to produce 2,3- pentanediones as raw material with it
The production process route of bar cleaning.
The document synthesized by the current lactic acid of induction-arrangement, it is found that lactic acid synthesis mainly has micro bioenzyme catalysis and chemistry to urge
Two kinds of change method.Its raw material for preparing lactic acid has cellulose, hemicellulose in cornstarch, leaf, stalk, grass etc..Just because of
The raw material for preparing lactic acid is inexpensive, along with the fermentation method technology maturation in synthesizing lactic acid method, therefore, lactic acid it is cheap.
How the value of lactic acid is liftedThe intensive processing of lactic acid is current preferable selection.
Lactic acid condensation reaction prepares 2, though 3- pentanediones have a small amount of document report, the activity of used catalyst is not high, and
And most of catalytic stabilities that lack are investigated.Designed catalyst of tracing it to its cause more protrudes the alkalescence (matching of catalyst
The decarboxylic reaction of condensation course), it have ignored the acidity (dehydration of matching condensation course) of catalyst.Therefore, it is designed
The soda acid property of catalyst is mismatched with the soda acid position needed for catalysis lactic acid condensation course, its result be exactly catalyst performance compared with
Difference.
The content of the invention
The characteristics of present invention is directed to lactic acid condensation reaction, i.e. concerted acid-base catalysis, devise barium pyrophosphate load caesium
Catalyst, the acidity on barium pyrophosphate surface contributes to dehydration, and the alkalescence of introduced caesium species contributes to decarboxylic reaction.Cause
This, constructed barium pyrophosphate load cesium-promoted catalyst illustrates good catalysis in lactic acid condensation prepares the reaction of 2,3- pentanediones
Performance.
A kind of barium pyrophosphate loads the preparation method of cesium-promoted catalyst, comprises the following steps：
Step one：The preparation of carrier
Barium nitrate is dissolved in distilled water and is sufficiently stirred for 30min, suction filtration after diammonium hydrogen phosphate stirring 2h is added, with distillation
It is transferred to after water washing in 120 DEG C of baking oven and dries 10h；In 500 DEG C of Muffle kiln roasting 3h, corresponding carrier is obtained；
Step 2：Amount according to barium ions and cesium ion material takes the barium pyrophosphate and nitre of respective quality in certain proportion
Sour caesium is dissolved in distilled water, is evaporated in 80 DEG C of oil bath pan, in 600 DEG C of Muffle kiln roasting 3h, that is, obtains corresponding
Catalyst.
Further, preparation method as described above, the ratio between the amount of material of the barium ions and cesium ion is 2.5：
0.5-1.25。
Further, the mass ratio of preparation method as described above, barium nitrate described in step one and diammonium hydrogen phosphate is
15.68：6.34.
As above the barium pyrophosphate load cesium-promoted catalyst that either method is prepared.
A kind of barium pyrophosphate load cesium-promoted catalyst is condensed the application in preparing 2,3- pentanedione techniques in lactic acid.
Application as described above, by Catalyst packing described above in quartz ampoule, carries lactic acid aqueous solution with nitrogen and leads to
Cross in the above-mentioned quartz ampoule for installing catalyst, using bio-based lactic acid as raw material, carrier gas is nitrogen, and reaction temperature is 270~340
DEG C, lactic acid concn is 5~35wt%, and charging rate is 1.13-2.26g/h, and the flow velocity of carrier gas is prepared for 0.4~5.0mL/min
2,3- pentanediones.
Further, application as described above, the flow velocity of carrier gas is 0.8mL/min.
Further, application as described above, lactic acid concn is 20-30wt%.
Further, application as described above, reaction temperature is 300-320 DEG C.
Beneficial effect：
By experimental studies have found that, lactic acid condensation reaction is soda acid concerted catalysis process, builds suitable soda acid bit distribution,
It is the key for improving catalyst performance, and barium pyrophosphate load cesium-promoted catalyst prepared by the inventive method, it is suitable that surface had both had
Acidic site also there are suitable basic sites, thus there are in catalysis lactic acid condensation prepares 2,3- pentanedione techniques good 2,
3- pentanediones selectivity and stability (28 hours, as shown in Figure 8).For example the ratio between amount of barium ions and cesium ion material is 2.5:
1 catalyst, at 300 DEG C, the conversion ratio of lactic acid is more than 90%, and the selectivity of 2,3- pentanediones is more than 50%, and catalyst connects
Reforwarding row 28h, the selectivity of catalyst is almost unchanged, therefore, and the catalyst activity that provides of the present invention is high, stability is good and 2,
The high conversion rate of 3- pentanediones selectivity and lactic acid, there is very high commercial development value, and burnt phosphorus of the present invention
The preparation method of sour barium load cesium-promoted catalyst is simple, and environmental protection is with low cost.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the barium pyrophosphate support type cesium-promoted catalyst of embodiment one；
Fig. 2 is the X-ray powder diffraction figure that the barium pyrophosphate of embodiment one loads cesium-promoted catalyst；
Fig. 3 is the scanning electron microscope (SEM) photograph that the barium pyrophosphate of embodiment one loads cesium-promoted catalyst；
Fig. 4 is the scanning electron microscope (SEM) photograph of the barium pyrophosphate catalyst of comparative examples 1；
Fig. 5 is the scanning electron microscope (SEM) photograph that the barium pyrophosphate of comparative examples 2 loads cesium-promoted catalyst；
Fig. 6 is the scanning electron microscope (SEM) photograph that the barium pyrophosphate of comparative examples 3 loads cesium-promoted catalyst；
Fig. 7 is the scanning electron microscope (SEM) photograph that the barium pyrophosphate of comparative examples 4 loads cesium-promoted catalyst；
Fig. 8 is barium pyrophosphate load cesium-promoted catalyst stability experiment result.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below technical scheme in the present invention carry out it is clear
Chu, it is fully described by, it is clear that described embodiment is a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
The present invention is an example of lactic acid intensive processing, i.e. the catalyst of lactic acid condensation reaction preparation 2,3- pentanediones is opened
Hair and technique.Synthesized specifically, the present invention is the method calcined on barium nitrate, ammonium dihydrogen phosphate and cesium nitrate by two steps
Barium pyrophosphate load cesium-promoted catalyst, and preparation method thereof and lactic acid be condensed prepare 2,3- pentanedione techniques in application.One
Typical example：Take 15.68g barium nitrates to be dissolved in 300mL distilled water and be sufficiently stirred for 30min, then add into solution 6.34g
Suction filtration after diammonium hydrogen phosphate stirring reaction 2h, is precipitated 3 times with distillation water washing, is transferred in 120 DEG C of baking oven and dries 10h.This
After be placed in Muffle furnace and be calcined 3h at 500 DEG C, obtain barium pyrophosphate carrier.Then, obtained barium pyrophosphate is made
For carrier, barium pyrophosphate support type cesium catalyst is prepared using infusion process.It can be prepared by modulation Ba2+ and Cs+ mol ratio
A series of barium pyrophosphate different loads amount cesium catalysts.Using bio-based lactic acid as raw material, carrier gas is nitrogen, and reaction temperature is
270~340 DEG C, lactic acid concn is 5~35wt%, and charging rate is 1~5mL/min, and the flow velocity of carrier gas is 0.4~5.0mL/
min.At 300 DEG C, the conversion ratio of lactic acid is more than 90%, and the selectivity of 2,3- pentanediones is more than 50%, and catalyst is continuously run
28h, the selectivity of catalyst is almost unchanged.A kind of barium pyrophosphate load cesium-promoted catalyst of the present invention prepares simple, green ring
Protect, with low cost, catalytic activity is high, and stability is good.
Embodiment one
15.68g barium nitrates, which are dissolved in 300mL distilled water, is sufficiently stirred for 30min, adds 6.34g diammonium hydrogen phosphates and stirs
Suction filtration after 2h is mixed, with water washing is distilled 3 times, is transferred in 120 DEG C of baking oven and dries 10h.In 500 DEG C of Muffle kiln roasting
3h, obtains corresponding carrier.The ratio between amount according to barium ions and cesium ion material is 2.5:1 take respective quality barium pyrophosphate and
Cesium nitrate is dissolved in 20mL distilled water, is evaporated in 80 DEG C of oil bath pan, in 600 DEG C of Muffle kiln roasting 3h, is produced
To corresponding catalyst.From a long 400mm, internal diameter is 4mm quartz ampoule, and the above-mentioned preparing catalysts of 0.30g are loaded on
In quartz ampoule, length of the catalyst in pipe is 30mm, and catalyst two ends are blocked with silica wool.Lactic acid is carried with nitrogen water-soluble
Liquid is by the way that in the above-mentioned quartz ampoule for installing catalyst, 5 DEG C/min temperature programmings are to 300 DEG C, and lactic acid concn is 20wt%, nitrogen
Flow velocity is 0.8mL/min, and charging lactic acid aqueous solution speed is 1.63g/h.Fig. 1 is the infrared of barium pyrophosphate support type cesium-promoted catalyst
Spectrogram；Fig. 2 is the X-ray powder diffraction figure that barium pyrophosphate loads cesium-promoted catalyst；Can be seen that cesium component by Fig. 1, Fig. 2 has
Effect has been loaded on barium pyrophosphate carrier, forms barium pyrophosphate loaded catalyst.Exactly because the load of cesium component, is just produced
Good soda acid bit distribution is given birth to, so that catalyst is provided with good catalytic performance.
Comparative examples 1
15.68g barium nitrates, which are dissolved in 300mL distilled water, is sufficiently stirred for 30min, adds 6.34g diammonium hydrogen phosphates and stirs
Suction filtration after 2h is mixed, with water washing is distilled 3 times, is transferred in 120 DEG C of baking oven and dries 10h.In 500 DEG C of Muffle kiln roasting
3h, obtains corresponding carrier.
Comparative examples 2
15.68g barium nitrates, which are dissolved in 300mL distilled water, is sufficiently stirred for 30min, adds 6.34g diammonium hydrogen phosphates and stirs
Suction filtration after 2h is mixed, with water washing is distilled 3 times, is transferred in 120 DEG C of baking oven and dries 10h.In 500 DEG C of Muffle kiln roasting
3h, obtains corresponding carrier.The ratio between amount according to barium ions and cesium ion material is 2.5:0.5 takes the barium pyrophosphate of respective quality
It is dissolved in 20mL distilled water, is evaporated in 80 DEG C of oil bath pan with cesium nitrate, in 600 DEG C of Muffle kiln roasting 3h, i.e.,
Obtain corresponding catalyst.From a long 400mm, internal diameter is 4mm quartz ampoule, and the above-mentioned preparing catalysts of 0.30g are loaded
In quartz ampoule, length of the catalyst in pipe is 30mm, and catalyst two ends are blocked with silica wool.Lactic acid water is carried with nitrogen
Solution is by the way that in the above-mentioned quartz ampoule for installing catalyst, 5 DEG C/min temperature programmings are to 300 DEG C, and lactic acid concn is 20wt%, nitrogen
Flow velocity be 0.8mL/min, charging lactic acid aqueous solution speed is 1.63g/h.Fig. 5 is the barium phosphate support type caesium of comparative examples 2
The scanning electron microscope (SEM) photograph of catalyst；
Comparative examples 3
15.68g barium nitrates, which are dissolved in 300mL distilled water, is sufficiently stirred for 30min, adds 6.34g diammonium hydrogen phosphates and stirs
Suction filtration after 2h is mixed, with water washing is distilled 3 times, is transferred in 120 DEG C of baking oven and dries 10h.In 500 DEG C of Muffle kiln roasting
3h, obtains corresponding carrier.The ratio between amount according to barium ions and cesium ion material is 2.5:1.25 take the pyrophosphoric acid of respective quality
Barium and cesium nitrate are dissolved in 20mL distilled water, are evaporated in 80 DEG C of oil bath pan, in 600 DEG C of Muffle kiln roasting 3h,
Obtain corresponding catalyst.From a long 400mm, internal diameter is 4mm quartz ampoule, and the above-mentioned preparing catalysts of 0.30g are filled
Fill in quartz ampoule, length of the catalyst in pipe is 30mm, and catalyst two ends are blocked with silica wool.Lactic acid is carried with nitrogen
The aqueous solution is by the way that in the above-mentioned quartz ampoule for installing catalyst, 5 DEG C/min temperature programmings are to 300 DEG C, and lactic acid concn is 20wt%, nitrogen
The flow velocity of gas is 0.8mL/min, and charging lactic acid aqueous solution speed is 1.63g/h.
Comparative examples 4
15.68g barium nitrates, which are dissolved in 300mL distilled water, is sufficiently stirred for 30min, adds 6.34g diammonium hydrogen phosphates and stirs
Suction filtration after 2h is mixed, with water washing is distilled 3 times, is transferred in 120 DEG C of baking oven and dries 10h.In 500 DEG C of Muffle kiln roasting
3h, obtains corresponding carrier.The ratio between amount according to barium ions and cesium ion material is 2.5:1.5 take the barium pyrophosphate of respective quality
It is dissolved in 20mL distilled water, is evaporated in 80 DEG C of oil bath pan with cesium nitrate, in 600 DEG C of Muffle kiln roasting 3h, i.e.,
Obtain corresponding catalyst.From a long 400mm, internal diameter is 4mm quartz ampoule, and the above-mentioned preparing catalysts of 0.30g are loaded
In quartz ampoule, length of the catalyst in pipe is 30mm, and catalyst two ends are blocked with silica wool.Lactic acid water is carried with nitrogen
Solution is by the way that in the above-mentioned quartz ampoule for installing catalyst, 5 DEG C/min temperature programmings are to 300 DEG C, and lactic acid concn is 20wt%, nitrogen
Flow velocity be 0.8mL/min, charging lactic acid aqueous solution speed is 1.63g/h.
Barium pyrophosphate prepared by different rate of charges loads the expression activitiy of cesium-promoted catalyst
The structure and properties of the barium pyrophosphate support type caesium prepared first to different rate of charges are characterized, as a result such as table
Shown in 1.From analysis test result, different rate of charges have certain influence to the physical property of catalyst with structure.
The catalytic performance of catalyst prepared by four different rate of charges is as shown in table 2.By the choosing of the conversion ratio and 2,3- pentanediones of lactic acid
Selecting property understands that the catalyst of different rate of charges has drawn 2, the 3- pentanediones selectivity in inconsistent result, embodiment one
Better than case of comparative examples, the different rate of charges of this explanation catalyst have a significant impact effect to the performance of catalyst.
The barium pyrophosphate that table 1 is obtained with different rate of charges loads the physical property of cesium-promoted catalyst
The barium pyrophosphate of table 2 loads the catalytic performance of cesium-promoted catalyst
Fig. 3 is the scanning electron microscope (SEM) photograph that the barium pyrophosphate of embodiment one loads cesium-promoted catalyst；Fig. 4 is the pyrophosphoric acid of comparative examples 1
Barium loads the scanning electron microscope (SEM) photograph of cesium-promoted catalyst；Fig. 5 is the ESEM of the barium pyrophosphate support type cesium-promoted catalyst of comparative examples 2
Figure；Fig. 6 is the scanning electron microscope (SEM) photograph of the barium pyrophosphate support type cesium-promoted catalyst of comparative examples 3；Fig. 7 is the pyrophosphoric acid of comparative examples 4
The scanning electron microscope (SEM) photograph of barium support type cesium-promoted catalyst；Illustrate that barium pyrophosphate is loaded after cesium component by Fig. 3-Fig. 7, the shape of catalyst
Looks have obvious difference.And observed by scanning electron microscopic picture, cesium component distribution is more uniform；Better catalytic activity, shows
Preparation method of the present invention is feasible.
Following examples are that barium pyrophosphate loads application of the cesium-promoted catalyst in lactic acid condensation prepares 2,3- pentanediones.
Embodiment two
0.3g particle diameters are placed in the quartz ampoule that internal diameter is 4mm in the barium pyrophosphate load cesium-promoted catalyst of 20~40 mesh, use stone
English cotton fixes the catalyst, and the quartz ampoule that then will be filled with catalyst is placed in heating furnace, opens nitrogen and logical with 0.8mL/min
Enter, open heater, be that temperature reaches 320 DEG C in the way of 5 DEG C/min temperature programmings, steady temperature, 1.63g/h is passed through
20% lactic acid aqueous solution, product is collected with the mode of ice-water bath, and product is yellow liquid, analyzes product, lactic acid
Conversion ratio is 92.2%, and the selectivity of 2,3- pentanediones is 49.4%.
Embodiment three
0.29g particle diameters are placed in the quartz ampoule that internal diameter is 4mm in the barium pyrophosphate load cesium-promoted catalyst of 20~40 mesh, use stone
English cotton fixes the catalyst, and the quartz ampoule that then will be filled with catalyst is placed in heating furnace, opens nitrogen and logical with 0.8mL/min
Enter, open heater, be that temperature reaches 280 DEG C in the way of 5 DEG C/min temperature programmings, steady temperature, 1.63g/h is passed through
20% lactic acid aqueous solution, product is collected with the mode of ice-water bath, and product is yellow liquid, analyzes product, lactic acid
Conversion ratio is 78.4%, and the selectivity of 2,3- pentanediones is 67.1%.
Example IV
0.29g particle diameters are placed in the quartz ampoule that internal diameter is 4mm in the barium pyrophosphate load cesium-promoted catalyst of 20~40 mesh, use stone
English cotton fixes the catalyst, and the quartz ampoule that then will be filled with catalyst is placed in heating furnace, opens nitrogen and logical with 0.8mL/min
Enter, open heater, be that temperature reaches 300 DEG C in the way of 5 DEG C/min temperature programmings, steady temperature, 1.63g/h is passed through
10% lactic acid aqueous solution, product is collected with the mode of ice-water bath, and product is yellow liquid, analyzes product, lactic acid
Conversion ratio is 84.2%, and the selectivity of 2,3- pentanediones is 45.0%.
Embodiment five
0.30g particle diameters are placed in the quartz ampoule that internal diameter is 4mm in the barium pyrophosphate load cesium-promoted catalyst of 20~40 mesh, use stone
English cotton fixes the catalyst, and the quartz ampoule that then will be filled with catalyst is placed in heating furnace, opens nitrogen and logical with 0.8mL/min
Enter, open heater, be that temperature reaches 300 DEG C in the way of 5 DEG C/min temperature programmings, steady temperature, 1.63g/h is passed through
30% lactic acid aqueous solution, product is collected with the mode of ice-water bath, and product is yellow liquid, analyzes product, lactic acid
Conversion ratio is 86.0%, and the selectivity of 2,3- pentanediones is 66.8%.
Embodiment six
0.29g particle diameters are placed in the quartz ampoule that internal diameter is 4mm in the barium pyrophosphate load cesium-promoted catalyst of 20~40 mesh, use stone
English cotton fixes the catalyst, and the quartz ampoule that then will be filled with catalyst is placed in heating furnace, opens nitrogen and with 0.25mL/min
It is passed through, opens heater, be that temperature reaches 300 DEG C in the way of 5 DEG C/min temperature programmings, steady temperature, 1.13g/h is passed through
20% lactic acid aqueous solution, product is collected with the mode of ice-water bath, and product is yellow liquid, analyzes product, lactic acid
Conversion ratio is 95.3%, and the selectivity of 2,3- pentanediones is 60.0%.
Embodiment seven
0.29g particle diameters are placed in the quartz ampoule that internal diameter is 4mm in the barium pyrophosphate load cesium-promoted catalyst of 20~40 mesh, use stone
English cotton fixes the catalyst, and the quartz ampoule that then will be filled with catalyst is placed in heating furnace, opens nitrogen and logical with 1.5mL/min
Enter, open heater, be that temperature reaches 300 DEG C in the way of 5 DEG C/min temperature programmings, steady temperature, 2.26g/h is passed through
20% lactic acid aqueous solution, product is collected with the mode of ice-water bath, and product is yellow liquid, analyzes product, lactic acid
Conversion ratio is 93.3%, and the selectivity of 2,3- pentanediones is 57.5%.
Embodiment eight
0.30g particle diameters are placed in the quartz ampoule that internal diameter is 4mm in the barium pyrophosphate load cesium-promoted catalyst of 20~40 mesh, use stone
English cotton fixes the catalyst, and the quartz ampoule that then will be filled with catalyst is placed in heating furnace, opens nitrogen and logical with 0.8mL/min
Enter, open heater, be that temperature reaches 300 DEG C in the way of 5 DEG C/min temperature programmings, steady temperature, 1.63g/h is passed through
20% lactic acid aqueous solution, catalyst is continuously run after 28h, and the conversion ratio of lactic acid is reduced to 86.4%, the choosing of 2,3- pentanediones
Selecting property is 55.7%.
To sum up illustrate, the change of barium pyrophosphate support type caesium prepared by the present invention to reaction environment has very strong adaptability,
The acute variation of reaction condition can be born, when flow rate of carrier gas, charging rate change, the conversion of lactic acid only occurs slightly
Fluctuation.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic；
And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical scheme spirit and
Scope.
Claims (9)
1. a kind of preparation method of barium pyrophosphate support type cesium-promoted catalyst, it is characterised in that comprise the following steps：
Step one：The preparation of carrier
Barium nitrate is dissolved in distilled water and is sufficiently stirred for 30min, suction filtration after diammonium hydrogen phosphate stirring 2h is added, is washed with distillation
It is transferred to after washing in 120 DEG C of baking oven and dries 10h；In 500 DEG C of Muffle kiln roasting 3h, corresponding carrier is obtained；
Step 2：Amount according to barium ions and cesium ion material takes the barium pyrophosphate and cesium nitrate of respective quality in certain proportion
It is dissolved in distilled water, is evaporated in 80 DEG C of oil bath pan, in 600 DEG C of Muffle kiln roasting 3h, i.e., is catalyzed accordingly
Agent.
2. preparation method according to claim 1, it is characterised in that the ratio between amount of material of the barium ions and cesium ion
For 2.5：0.5-1.25.
3. preparation method according to claim 1, it is characterised in that barium nitrate described in step one and diammonium hydrogen phosphate
Mass ratio is 15.68：6.34.
4. the barium pyrophosphate prepared according to claim 1-3 either method loads cesium-promoted catalyst.
5. a kind of barium pyrophosphate load cesium-promoted catalyst is condensed the application in preparing 2,3- pentanedione techniques in lactic acid.
6. application according to claim 5, it is characterised in that by Catalyst packing described in claim 4 in quartz ampoule,
Lactic acid aqueous solution is carried by the above-mentioned quartz ampoule for installing catalyst with nitrogen, using bio-based lactic acid as raw material, carrier gas is nitrogen
Gas, reaction temperature is 270~340 DEG C, and lactic acid concn is 5~35wt%, and charging rate is 1.13-2.26g/h, the flow velocity of carrier gas
2,3- pentanediones are prepared for 0.4~5.0mL/min.
7. application according to claim 6, it is characterised in that the flow velocity of carrier gas is 0.8mL/min.
8. application according to claim 6, it is characterised in that lactic acid concn is 20-30wt%.
9. application according to claim 6, it is characterised in that reaction temperature is 300-320 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN108246320A (en) * | 2018-01-08 | 2018-07-06 | 重庆理工大学 | A kind of catalyst and preparation method thereof, application |
| CN114604839A (en) * | 2022-03-15 | 2022-06-10 | 贵州胜威凯洋化工有限公司 | Preparation method of barium pyrophosphate |
| CN114604840A (en) * | 2022-03-15 | 2022-06-10 | 贵州胜威凯洋化工有限公司 | Preparation method of barium pyrophosphate based on barium hydrogen phosphate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107556250A (en) * | 2017-08-07 | 2018-01-09 | 东莞市联洲知识产权运营管理有限公司 | The high-efficiency synthesis method of the methylpyrazine of 2 ethyl 3 |
| CN108246320A (en) * | 2018-01-08 | 2018-07-06 | 重庆理工大学 | A kind of catalyst and preparation method thereof, application |
| CN108246320B (en) * | 2018-01-08 | 2020-12-15 | 重庆理工大学 | Catalyst, and preparation method and application thereof |
| CN114604839A (en) * | 2022-03-15 | 2022-06-10 | 贵州胜威凯洋化工有限公司 | Preparation method of barium pyrophosphate |
| CN114604840A (en) * | 2022-03-15 | 2022-06-10 | 贵州胜威凯洋化工有限公司 | Preparation method of barium pyrophosphate based on barium hydrogen phosphate |
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