CN106111148A - A kind of preparation of copper bismuth/SiO 2 catalyst - Google Patents
A kind of preparation of copper bismuth/SiO 2 catalyst Download PDFInfo
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- CN106111148A CN106111148A CN201610476938.XA CN201610476938A CN106111148A CN 106111148 A CN106111148 A CN 106111148A CN 201610476938 A CN201610476938 A CN 201610476938A CN 106111148 A CN106111148 A CN 106111148A
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- copper
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- bismuth
- sio
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
Invention relates to the preparation of a kind of copper bismuth/SiO 2 catalyst.It is characterized in that being prepared for copper bismuth/SiO 2 catalyst with " one kettle way ", copper oxide content is 10 40%, and bi content is 1 10%, and remaining is silicon dioxide.Copper bismuth species high dispersive, at silicon dioxide surfaces externally and internally, improves the reaction center of catalyst, enhances the wearability of catalyst, decreases the precipitation degree of copper ion.In the application of alkynes aldehyde reaction synthesis Isosorbide-5-Nitrae butynediols, copper bismuth catalyst activity is good, and selectivity is high, and copper species precipitation amount is relatively low.
Description
Technical field
The present invention relates to a kind of copper bismuth catalyst producing Isosorbide-5-Nitrae-butynediols, be to prepare copper bismuth/dioxy with " one kettle way "
SiClx catalyst and the application in alkynes aldehyde reaction.
Background technology
Copper bismuth catalyst catalyzing acetylene and formaldehyde can generate 1,4-butynediols in alkynes aldehyde reaction.1,4-butine
Glycol generation hydrogenation reaction can be converted into 1,4-butanediol.BDO is important Organic Chemicals, by dehydrogenation and
The reactions such as dehydration can prepare a series of downstreams chemical products, such as polybutylene terephthalate (PBT) (PBT), gamma-butyrolacton
(GBL), polyurethane (PU), N-Methyl pyrrolidone (NMP), oxolane (THF) and polytetramethylene glycol ether (PTMEG)
Deng.Owing to BDO has the higher added value of industry, its demand sustainable growth.Industrialized production 1,4-butynediols
Technique mainly improvement alkynes aldehyde method (Reppe method), such as companies such as domestic Shanxi three-dimensional, sky, Sichuan China, Xinjiang Meike chemical industry
All use this kind of technology.Improvement Reppe method technique, under normal pressure or lower pressure, carries out alkynes aldehyde in slurry bed or suspension bed
Change reaction, the performance of catalyst is proposed high requirement.At present, disclosed patent such as US4127734 and US4584418,
CN1118342A, respectively with DNAcarrier free malachite, carrier-free copper oxide/bismuth oxide, carry out anti-under the conditions of improved process
Should, it is active that these catalyst have certain catalysis, but poor catalyst stability, the most wear-resistant, copper species easily run off.Pin
To this situation, occur in that the ethynylation catalyst with silicon dioxide, silica gel, aluminium sesquioxide, molecular sieve as carrier.Such as patent
US3920759 and CN102125856A, individually discloses the copper bismuth loaded catalyst with magnesium silicate, Kaolin as carrier, uses
The catalytic reaction of 1,4-butynediols is synthesized with formaldehyde and acetylene.But such catalyst has the disadvantage that (1) carrier silicic acid
Magnesium is unstable, can dissolve in reaction system, and the life-span is short；(2) interaction between carrier and copper species is more weak, copper thing
Plant precipitation higher；(3) catalyst preparation process is complicated, is unfavorable for that industrialized developing uses.
Summary of the invention
It is an object of the invention to overcome defect present in above-mentioned prior art, it is provided that copper prepared by a kind of " one kettle way "
Bismuth/SiO 2 catalyst, and in suspension bed, synthesize Isosorbide-5-Nitrae-butynediols for formaldehyde and acetylene.Catalyst stability is good,
Activity is good, and the precipitation of copper species relatively carrier-free copper bismuth catalyst decreases.
The catalyst of the present invention is copper bismuth/SiO 2 catalyst that a kind of alkynes aldehyde method produces Isosorbide-5-Nitrae-butynediols, and it is special
Levying and be: copper oxide is main active component, its mass content is 10%～40%, and bismuth oxide is auxiliary agent, its mass content be 1%～
10%, remaining is silicon dioxide.
A kind of alkynes aldehyde method of the present invention produces the copper bismuth/SiO 2 catalyst of Isosorbide-5-Nitrae-butynediols, it is characterised in that:
Used catalyst granular size is 20～60 um.
The alkynes aldehyde method of the present invention produces the copper bismuth/SiO 2 catalyst of Isosorbide-5-Nitrae-butynediols, makes by the following method
Standby: first a certain amount of mantoquita and bismuth salt to be dissolved in distilled water, and drip a certain amount of surfactant, mix homogeneously.Separately
The aqueous solution being dissolved with cetyl trimethylammonium bromide and sodium silicate is added in above-mentioned copper bismuth mixed solution, stirs.
Finally, precipitant rapidly joining above-mentioned mixed solution, adjusting pH value is 9～10.After mixed liquor 8～24 h is stirred at room temperature,
Centrifugation, washes 3 times, then with absolute ethanol washing 2 times, i.e. obtains copper bismuth/dioxy in 550 DEG C of roastings 5～8 h after drying at room temperature
SiClx catalyst.
The alkynes aldehyde method of the present invention produces the copper bismuth/SiO 2 catalyst of 1,4-butynediols, enhances copper bismuth species
With the interaction of silicon dioxide, effectively reduce the precipitation of copper species, improve the stability of catalyst.
The alkynes aldehyde method of the present invention produces the copper bismuth/SiO 2 catalyst of Isosorbide-5-Nitrae-butynediols, and preparation process is simple,
Grain size is uniform, keeps preferably being catalyzed activity.
Detailed description of the invention
Embodiment 1
Weigh 9.0 g cetyl trimethylammonium bromide (CTAB) and 28.5 g Na respectively2SiO3·10H2O is dissolved in 250 mL
In water.Weigh 7.2 g Cu (NO again3)2·3H2O and 0.8 g Bi (NO3)3·5H2O is dissolved in 50 mL water, adds the 5 poly-second of mL
Glycol 400, rapidly joins 10 mL strong aqua ammonia, stirs 0.5 h.Copper bismuth mixed liquor is joined above-mentioned containing CTAB and sodium silicate
In solution, after stirring 0.5 h, use 1 mol/LH2SO4Regulation solution ph is 9-10, centrifugation after stirring at normal temperature 3-24 h,
Use distilled water and absolute ethanol washing repeatedly respectively, after drying at room temperature, place 550 DEG C of roasting 5 h in high temperature furnace and obtain copper bismuth/bis-
Silicon oxide catalyst.Taking the above-mentioned catalyst prepared and carry out alkynes aldehyde reaction, after reacting 7 h, formaldehyde conversion is 66%, 1,
The selectivity of 4-butynediols is 91%, and after reaction, in filtrate, content of copper ion is 24 ug/mL.
Embodiment 2
Weigh 10.0 g cetyl trimethylammonium bromide (CTAB) respectively and 25.0 g tetraethyl orthosilicates are dissolved in 100 mL second
In alcohol-water solution.Weigh 7.2 g Cu (NO again3)2·3H2O and 0.8 g Bi (NO3)3·5H2O is dissolved in 50 mL water, adds 5
ML PEG400, rapidly joins 10 mL strong aqua ammonia, stirs 0.5 h.Copper bismuth mixed liquor is joined above-mentioned containing CTAB and just
In the solution of silester, after stirring 0.5 h, use 1 mol/LH2SO4Regulation pH value is 9-10, centrifugal after stirring at normal temperature 3-24 h
Separate, use distilled water and absolute ethanol washing repeatedly respectively, after drying at room temperature, place 550 DEG C of roasting 5 h in high temperature furnace and obtain copper
Bismuth/SiO 2 catalyst.Taking the above-mentioned catalyst prepared and carry out alkynes aldehyde reaction, after reacting 7 h, formaldehyde conversion is
67%, the selectivity of Isosorbide-5-Nitrae-butynediols is 90%, and after reaction, in filtrate, content of copper ion is 20 ug/mL.
Embodiment 3
Weigh 10.0 g lauryl amines (DDA) respectively and 25.0 g tetraethyl orthosilicates are dissolved in 100 mL ethanol solution.Weigh again
5.1 g CuCl2·2H2O and 0.8 g Bi (NO3)3·5H2O is dissolved in 30 mL water, adds 5 mL PEG400s, quickly adds
Enter 10 mL strong aqua ammonia, stir 0.5 h.Copper bismuth mixed liquor is joined in the above-mentioned solution containing CTAB and tetraethyl orthosilicate, stirs
After mixing 0.5 h, use 1 mol/LH2SO4Regulation pH value is 9-10, centrifugation after stirring at normal temperature 3-24 h, respectively with distilled water and
Absolute ethanol washing repeatedly, after drying at room temperature, is placed 550 DEG C of roasting 5 h in high temperature furnace and is obtained copper bismuth/SiO 2 catalyst.
Taking the above-mentioned catalyst prepared and carry out alkynes aldehyde reaction, after reacting 7 h, formaldehyde conversion is 60%, Isosorbide-5-Nitrae-butynediols
Selectivity is 94%, and after reaction, in filtrate, content of copper ion is 21 ug/mL.
Embodiment 4
Weigh 9.0 g cetyl trimethylammonium bromide (CTAB) and 28.5 g Na respectively2SiO3·10H2O is dissolved in 250 mL
In water.Weigh 5.39 g Cu (CH again3COO)2·H2O and 0.8 g Bi (NO3)3·5H2O is dissolved in 30 mL water, adds 5 mL
PEG400, rapidly joins 10 mL strong aqua ammonia, stirs 0.5 h.Copper bismuth mixed liquor is joined above-mentioned containing CTAB with silicic acid
In the solution of sodium, after stirring 0.5 h, use 1 mol/LH2SO4Regulation pH value is 9-10, centrifugation after stirring at normal temperature 3-24 h,
Use distilled water and absolute ethanol washing repeatedly respectively, after drying at room temperature, place 550 DEG C of roasting 5 h in high temperature furnace and obtain copper bismuth/bis-
Silicon oxide catalyst.Taking the above-mentioned catalyst prepared and carry out alkynes aldehyde reaction, after reacting 7 h, formaldehyde conversion is 62%, 1,
The selectivity of 4-butynediols is 90%, and after reaction, in filtrate, content of copper ion is 27 ug/mL.
Embodiment 5
Weigh 9.0 g cetyl trimethylammonium bromide (CTAB) and 28.5 g Na respectively2SiO3·10H2O is dissolved in 250 mL
In water.Weigh 5.0 g Cu (NO again3)2·3H2O and 0.45 g Bi (NO3)3·5H2O is dissolved in 30 mL water, adds 2 mL and gathers
Ethylene glycol 400, rapidly joins 5 mL strong aqua ammonia, stirs 0.5 h.Copper bismuth mixed liquor is joined above-mentioned containing CTAB with sodium silicate
Solution in, after stirring 0.5 h, use 1 mol/LH2SO4Regulation pH value is 9-10, centrifugation after stirring at normal temperature 3-24 h, point
Not Yong distilled water and absolute ethanol washing repeatedly, after drying at room temperature, place 550 DEG C of roasting 5 h in high temperature furnace and obtain copper bismuth/dioxy
SiClx catalyst.Taking the above-mentioned catalyst generation alkynes aldehyde reaction prepared, after reacting 7 h, formaldehyde conversion is 53%, 1,
The selectivity of 4-butynediols is 97%, and the content of copper ion in filtrate is 11 ug/mL.
Embodiment 6
Weigh 10.0 g lauryl amines (DDA) and 24.5 g Na respectively2SiO3·10H2O is dissolved in 100 mL ethanol waters.Again
Weigh 5.39 g Cu (CH3COO)2·H2O and 0.8 g Bi (NO3)3·5H2O is dissolved in 30 mL water, adds 5 mL Polyethylene Glycol
800, rapidly join 10 mL strong aqua ammonia, stir 0.5 h.Copper bismuth mixed liquor is joined above-mentioned containing CTAB with the solution of sodium silicate
In, after stirring 0.5 h, use 1 mol/LH2SO4Regulation pH value is 9-10, centrifugation after stirring at normal temperature 3-24 h, respectively with steaming
Distilled water and absolute ethanol washing repeatedly, after drying at room temperature, are placed 550 DEG C of roasting 5 h in high temperature furnace and are obtained copper bismuth/silicon dioxide and urge
Agent.Taking the above-mentioned catalyst prepared and carry out alkynes aldehyde reaction, after reacting 7 h, formaldehyde conversion is 59%, Isosorbide-5-Nitrae-butine
The selectivity of glycol is 88%, and after reaction, in filtrate, content of copper ion is 31 ug/mL.
Embodiment 7
Weigh 7.5 g lauryl amines respectively and 20.6 g tetraethyl orthosilicates are dissolved in 100 mL ethanol.Weigh 7.2 g Cu again
(NO3)2·3H2O and 0.8 g Bi (NO3) 3·5H2O is dissolved in 50 mL water, adds 5 mL PEG400s, rapidly joins 10
ML strong aqua ammonia, stirs 0.5 h.Copper bismuth mixed liquor is joined in the above-mentioned solution containing lauryl amine and tetraethyl orthosilicate, stirring
After 0.5 h, use 1 mol/LH2SO4Regulation pH value is 9-10, centrifugation after stirring at normal temperature 3-24 h, respectively by distilled water and nothing
Water-ethanol washs repeatedly, after drying at room temperature, places 550 DEG C of roasting 5 h in high temperature furnace and obtains copper bismuth catalyst.Take above-mentioned preparing
Catalyst carry out alkynes aldehyde reaction, after reacting 7 h, formaldehyde conversion is 64%, and the selectivity of Isosorbide-5-Nitrae-butynediols is 93%,
After reaction, in filtrate, content of copper ion is 19 ug/mL.
Claims (4)
1. the copper bismuth/SiO 2 catalyst for alkynes aldehyde reaction, it is characterised in that: use template with " one kettle way "
Agent, precipitant and surfactant are prepared for copper bismuth/SiO 2 catalyst, and this catalyst copper oxide is main active component, bismuth oxide
For auxiliary agent, wherein the mass content of copper oxide is 10%～40%, and the mass content of bismuth oxide is 1%～10%, and remaining content is two
Silicon oxide.
Copper bismuth/SiO 2 catalyst the most according to claim 1, it is characterised in that silicon source used be sodium silicate or
One in tetraethyl orthosilicate, template used dose is the one in cetyl trimethylammonium bromide or lauryl amine, used
Precipitant is the one in ammonia or sodium carbonate.
Copper bismuth/SiO 2 catalyst the most according to claim 1, it is characterised in that mantoquita used in preparation method
For any one in copper chloride, copper nitrate, Schweinfurt green；Bismuth salt used is any one in bismuth sulfate, bismuth chloride, bismuth nitrate
Kind.
Copper bismuth/SiO 2 catalyst the most according to claim 1, it is characterised in that surface used in preparation method
Activating agent is PEG400, polyethylene glycol-800, any one in polyvinylpyrrolidone.
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| CN201610476938.XA CN106111148A (en) | 2016-06-27 | 2016-06-27 | A kind of preparation of copper bismuth/SiO 2 catalyst |
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| CN201610476938.XA CN106111148A (en) | 2016-06-27 | 2016-06-27 | A kind of preparation of copper bismuth/SiO 2 catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109046231A (en) * | 2018-08-29 | 2018-12-21 | 合肥学院 | A kind of ultrasonic wave assisted hydrothermal synthesis method prepares the method and application of mesoporous cupric silicate bismuth nanocomposite |
| CN111841557A (en) * | 2020-08-29 | 2020-10-30 | 朱丽英 | Catalyst for producing 1, 4-butynediol and preparation method thereof |
-
2016
- 2016-06-27 CN CN201610476938.XA patent/CN106111148A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109046231A (en) * | 2018-08-29 | 2018-12-21 | 合肥学院 | A kind of ultrasonic wave assisted hydrothermal synthesis method prepares the method and application of mesoporous cupric silicate bismuth nanocomposite |
| CN109046231B (en) * | 2018-08-29 | 2020-12-22 | 合肥学院 | Method for preparing mesoporous copper bismuth silicate nano composite material by ultrasonic-assisted hydrothermal synthesis method and application |
| CN111841557A (en) * | 2020-08-29 | 2020-10-30 | 朱丽英 | Catalyst for producing 1, 4-butynediol and preparation method thereof |
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