CN102626637B - Catalyst for one-step preparation of epoxyethane from ethane, and preparation method thereof - Google Patents
Catalyst for one-step preparation of epoxyethane from ethane, and preparation method thereof Download PDFInfo
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- CN102626637B CN102626637B CN2012100740172A CN201210074017A CN102626637B CN 102626637 B CN102626637 B CN 102626637B CN 2012100740172 A CN2012100740172 A CN 2012100740172A CN 201210074017 A CN201210074017 A CN 201210074017A CN 102626637 B CN102626637 B CN 102626637B
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- salt
- catalyst
- yttrium
- nickel
- silver
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A catalyst for the one-step preparation of epoxyethane from ethane, and a preparation method thereof are provided. The catalyst is an Ag:Ni:Y oxygen composite catalyst, wherein the molar ratio of Ag:Ni:Y is 1:1:0.01-0.04. The preparation method comprises the following steps: adding deionized water to a silver salt, a nickel salt and an yttrium salt to prepare a mixed solution, and adding deionized water to citric acid to prepare a solution; adding the mixed solution of the silver salt, the nickel salt and the yttrium salt to the citric acid solution at 60DEG C under magnetic stirring, wherein the molar ratio of the silver salt to the nickel salt to the yttrium salt to the citric acid is 1:1:0.01-0.04:2.01-2.04; and adjusting the pH of the resulting solution to 1, continuously maintaining the magnetic stirring at 60DEG C until the solution forms a sticky colloid, drying the colloid at 130DEG C for 12h, and roasting the dried colloid in a muffle furnace at 400DEG C for 3h according to a heating rate of 2DEG C/min to obtain the required catalyst. The catalyst has the advantages of low reaction temperature and high reaction activity.
Description
Technical field
The present invention relates to a kind of chemical catalyst and preparation method thereof, particularly a kind of Catalysts and its preparation method for one step of ethane epoxy ethane.
Background technology
Oxirane is the important Organic chemical products that is only second to polyethylene and polyvinyl chloride in the ethylene industry derivative, is broad-spectrum organic synthesis intermediate, can obtain a series of very important fine chemical products by oxirane derivative.It is widely used in and produces ethylene glycol and other polyalcohols, also is used for the production of ethoxylate, monoethanolamine, solvent and the glycol ether of detergent industry.In addition, oxirane also can be used as the disinfectant of fumigant and medicine equipment etc.Along with the development of modern industry, both at home and abroad the demand of oxirane grown with each passing day.
Early stage ethylene oxide production adopts chlorohydrination technique, and the chlorohydrination course of reaction is: (1) ethanol dehydration, time chlorination of (2) ethene, (3) alkalization.Owing to producing a large amount of Halogen waste water in the chlorohydrination production process, environmental pollution is serious, so method is substantially inactive at present.At present, oxirane production technology generally adopts the direct oxidation of ethylene to method both at home and abroad, and wherein comparatively ripe production technology is in calandria type fixed bed reactor, uses silver catalyst, and adopting pure oxygen and ethene is that oxirane is produced in the raw material direct oxidation.Present industrial ethylene prepares the reaction temperature of oxirane generally between 200 ℃～300 ℃, ethane oxidation prepares the temperature of ethene usually more than 900 ℃, both temperature are mutually far short of what is expected, and are used for the silver that ethylene epoxidizing prepares the catalyst of oxirane and at high temperature easily make reaction that deep oxidation occurs.In present oxirane production technology, must first make ethene by ethane, then make oxirane by ethylene.
CN101265242A has introduced a kind of method of directly preparing epoxy ethane by ethane one-step oxidation, the Ag-Ni-O catalyst that employing makes with sluggish precipitation, the silver salt, nickel salt and the urea that take are according to a certain ratio put into container, add deionized water in container, with after seal of vessel 65～95 ℃ of lower magnetic force stirring reactions 4～12 hours, and then be placed in Muffle furnace, and after beginning to warm to 380 ℃～400 ℃ with the heating rate of 1～4 ℃/min from 100 ℃, roasting 2～4 hours.The reaction temperature that embodies catalyst activity is 250 ℃～390 ℃, but the reactivity of this catalyst is not high, and the selective and productive rate of oxirane is lower.
Summary of the invention
The objective of the invention is for existing Ag-Ni-O catalyst reaction activity not high, selective and the lower defective of productive rate of oxirane, a kind of preparation method who goes on foot the catalyst of epoxy ethane for ethane one is provided, the catalyst of the method preparation has advantages of that reaction temperature is low, reactivity is high, is used for the advantage that one step of ethane epoxy ethane can significantly improve the selective and productive rate of oxirane.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of catalyst for one step of ethane epoxy ethane, it is characterized in that: this catalyst is silver-colored nickel yttrium oxygen composite catalyst, and the containing element composition has Ag, Ni, Y, O, molar ratio Ag: Ni: Y=1: 1: 0.01～0.04.
A kind of catalyst for one step of ethane epoxy ethane, adopting silver salt, nickel salt, yttrium salt and citric acid is that raw material makes,
Concrete steps are:
The silver salt that takes, nickel salt, yttrium salt are put into container, add deionized water to make mixed solution in container, separately citric acid are put into another container and are added deionized water to make solution; The ratio of the amount of substance between silver salt, nickel salt, yttrium salt and citric acid is 1: 1: 0.01～0.04: 2.01～2.04;
In under 60 ℃ of magnetic agitation, the mixed solution of silver-colored nickel yttrium salt dropwise being joined citric acid solution, and transfer its PH=1 with nitric acid, continue to keep 60 ℃ of lower magnetic forces to stir, until solution forms thick colloid, then it was dried by the fire 12 hours under 130 ℃, be placed in again Muffle furnace with the heating rate of 2 ℃/min 400 ℃ of lower roastings 3 hours, namely get required catalyst.
Described silver salt, nickel salt, yttrium salt are silver nitrate, nickel nitrate, yttrium nitrate.
The catalyst of the present invention's preparation is used for the ethane oxidation step and directly makes oxirane.The process conditions of reporting in the process conditions that adopt and document before are close.The process conditions that Ag-Ni-Y-O of the present invention can adopt are: adopt tubular reactor, reaction temperature is at 280～340 ℃, and the proportioning of ethane and oxygen, nitrogen is 1: 1: 6, and gas space velocity is 12000mlg
-1H
-1
The key of the inventive method is the doping of auxiliary agent Y element and preparation method's improvement, and the Ag-Ni-Y-O composite catalyst that makes significantly improves than its reactivity of Ag-Ni-O catalyst before, and the selective and productive rate of oxirane is greatly improved.
The specific embodiment
Below in conjunction with embodiment, the present invention is made further and illustrating, but the present invention is not limited to these examples.
Comparative Examples 1
Take AgNO
31.6987g, Ni (NO
3)
26H
2O 2.9079g puts into beaker, adds the 10ml deionized water, separately takes C
6H
8O
7H
2O 4.2028g puts into another beaker, adds the 10ml deionized water, puts into little magneton after dissolving, under 60 ℃ of magnetic agitation with AgNO
3With Ni (NO
3)
26H
2The mixed solution of O dropwise joins in citric acid solution with glue head dropper, and transfer its PH=1 with nitric acid, keep 60 ℃ of lower magnetic forces to stir, until solution forms thick colloid, then dried by the fire 12 hours under 130 ℃, be placed in again Muffle furnace with the heating rate of 2 ℃/min 400 ℃ of lower roastings 3 hours, namely get catalyst.The catalyst that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed bed reactors of 5mm that tubular reactor adopts internal diameter, silver-colored nickel oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 290 ℃, and the flow-control of ethane, oxygen and nitrogen is at 5ml/min, 5ml/min and 30ml/min.Analysis result sees Table 1.
Embodiment 1
Take AgNO
31.6987g, Ni (NO
3)
26H
2O 2.9079g, Y (NO
3)
36H
2O 0.0383g puts into beaker, adds the 10ml deionized water, separately takes C
6H
8O
7H
2O 4.2238g puts into another beaker, adds the 10ml deionized water, puts into little magneton after dissolving, under 60 ℃ of magnetic agitation with AgNO
3, Ni (NO
3)
26H
2O and Y (NO
3)
36H
2The mixed solution of O dropwise joins in citric acid solution with glue head dropper, and transfer its PH=1 with nitric acid, keep 60 ℃ of lower magnetic forces to stir, until solution forms thick colloid, then dried by the fire 12 hours under 130 ℃, be placed in again Muffle furnace with the heating rate of 2 ℃/min 400 ℃ of lower roastings 3 hours, namely get catalyst.The catalyst that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed bed reactors of 5mm that tubular reactor adopts internal diameter, silver-colored nickel yttrium oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 290 ℃, and the flow-control of ethane, oxygen and nitrogen is at 5ml/min, 5ml/min and 30ml/min.Analysis result sees Table 1.
Embodiment 2
Take AgNO
31.6987g, Ni (NO
3)
26H
2O 2.9079g, Y (NO
3)
36H
2O 0.0766g puts into beaker, adds the 10ml deionized water, separately takes C
6H
8O
7H
2O 4.2448g puts into another beaker, adds the 10ml deionized water, puts into little magneton after dissolving, under 60 ℃ of magnetic agitation with AgNO
3, Ni (NO
3)
26H
2O and Y (NO
3)
36H
2The mixed solution of O dropwise joins in citric acid solution with glue head dropper, and transfer its PH=1 with nitric acid, keep 60 ℃ of lower magnetic forces to stir, until solution forms thick colloid, then dried by the fire 12 hours under 130 ℃, be placed in again Muffle furnace with the heating rate of 2 ℃/min 400 ℃ of lower roastings 3 hours, namely get catalyst.The catalyst that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed bed reactors of 5mm that tubular reactor adopts internal diameter, silver-colored nickel yttrium oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 290 ℃, and the flow-control of ethane, oxygen and nitrogen is at 5ml/min, 5ml/min and 30ml/min.Analysis result sees Table 1.
Embodiment 3
Take AgNO
31.6987g, Ni (NO
3)
26H
2O 2.9079g, Y (NO
3)
36H
2O 0.1149g puts into beaker, adds the 10ml deionized water, separately takes C
6H
8O
7H
2O 4.2658g puts into another beaker, adds the 10ml deionized water, puts into little magneton after dissolving, under 60 ℃ of magnetic agitation with AgNO
3, Ni (NO
3)
26H
2O and Y (NO
3)
36H
2The mixed solution of O dropwise joins in citric acid solution with glue head dropper, and transfer its PH=1 with nitric acid, keep 60 ℃ of lower magnetic forces to stir, until solution forms thick colloid, then dried by the fire 12 hours under 130 ℃, be placed in again Muffle furnace with the heating rate of 2 ℃/min 400 ℃ of lower roastings 3 hours, namely get catalyst.The catalyst that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed bed reactors of 5mm that tubular reactor adopts internal diameter, silver-colored nickel yttrium oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 290 ℃, and the flow-control of ethane, oxygen and nitrogen is at 5ml/min, 5ml/min and 30ml/min.Analysis result sees Table 1.
Embodiment 4
Take AgNO
31.6987g, Ni (NO
3)
26H
2O 2.9079g, Y (NO
3)
36H
2O 0.1532g puts into beaker, adds the 10ml deionized water, separately takes C
6H
8O
7H
2O 4.2869g puts into another beaker, adds the 10ml deionized water, puts into little magneton after dissolving, under 60 ℃ of magnetic agitation with AgNO
3, Ni (NO
3)
26H
2O and Y (NO
3)
36H
2The mixed solution of O dropwise joins in citric acid solution with glue head dropper, and transfer its PH=1 with nitric acid, keep 60 ℃ of lower magnetic forces to stir, until solution forms thick colloid, then dried by the fire 12 hours under 130 ℃, be placed in again Muffle furnace with the heating rate of 2 ℃/min 400 ℃ of lower roastings 3 hours, namely get catalyst.The catalyst that makes is used for the catalyst performance evaluation experiment, wherein: it is the miniature quartz pipe fixed bed reactors of 5mm that tubular reactor adopts internal diameter, silver-colored nickel yttrium oxygen composite catalyst 0.2g packs in reactor, the temperature of this reactor is controlled at 290 ℃, and the flow-control of ethane, oxygen and nitrogen is at 5ml/min, 5ml/min and 30ml/min.Analysis result sees Table 1.
What above-described embodiment adopted is silver nitrate, nickel nitrate, yttrium nitrate, and all the other silver salt, nickel salt, yttrium salt also are fit to this preparation method, do not enumerate herein.
Table 1 catalyst performance evaluation experiment analysis results
| The conversion ratio of ethane (%) | Selective (%) of oxirane | The productive rate of oxirane (%) | |
| Comparative Examples 1 | 26.6 | 5.3 | 1.4 |
| Embodiment 1 | 30.6 | 4.6 | 1.5 |
| Embodiment 2 | 32.3 | 19.3 | 6.3 |
| Embodiment 3 | 38.4 | 19.8 | 7.6 |
| Embodiment 4 | 27.9 | 4.1 | 1.2 |
Higher by the visible Ag-Ni-Y-O catalyst reaction of analysis result activity, ethane maximum conversion rate 38.4%, maximum ethane conversion 29.4% in the CN101265242A is significantly improved.In addition, the Ag-Ni-Y-O catalyst also improves a lot the selective and yield of oxirane for one step of ethane epoxy ethane.In CN101265242A, the best selective of oxirane is 13.2%, the oxirane optimum yields is 3.4%, and the best selective of its oxirane of catalyst of the present invention's preparation is 19.8%, the oxirane optimum yields is 7.6%, and catalyst is significantly increased the selective and productive rate of oxirane in the CN101265242A.
Claims (3)
1. one kind is used for the catalyst that ethane one goes on foot epoxy ethane, and it is characterized in that: this catalyst is silver-colored nickel yttrium oxygen composite catalyst, molar ratio Ag:Ni:Y=1:1:0.01～0.04, and the preparation method of this catalyst comprises the steps:
A, take a certain amount of silver salt, nickel salt, yttrium salt and put into container, add deionized water to make mixed solution in container, separately a certain amount of citric acid is put into another container and add deionized water to make solution;
B, under 60 ℃ of magnetic agitation, the mixed solution of silver, nickel, yttrium salt is dropwise joined citric acid solution, wherein the ratio of the amount of substance between silver salt, nickel salt, yttrium salt and citric acid is 1:1:0.01～0.04:2.01～2.04; And transfer its pH=1 with nitric acid, continue to keep 60 ℃ of lower magnetic forces to stir, until solution forms thick colloid, then it was dried by the fire 12 hours under 130 ℃, then be placed in Muffle furnace with the heating rate of 2 ℃/min 400 ℃ of lower roastings 3 hours, namely get required catalyst.
2. the preparation method of catalyst claimed in claim 1, is characterized in that comprising the steps:
A, take a certain amount of silver salt, nickel salt, yttrium salt and put into container, add deionized water to make mixed solution in container, separately a certain amount of citric acid is put into another container and add deionized water to make solution;
B, under 60 ℃ of magnetic agitation, the mixed solution of silver, nickel, yttrium salt is dropwise joined citric acid solution, wherein the ratio of the amount of substance between silver salt, nickel salt, yttrium salt and citric acid is 1:1:0.01～0.04:2.01～2.04; And transfer its pH=1 with nitric acid, continue to keep 60 ℃ of lower magnetic forces to stir, until solution forms thick colloid, then it was dried by the fire 12 hours under 130 ℃, then be placed in Muffle furnace with the heating rate of 2 ℃/min 400 ℃ of lower roastings 3 hours, namely get required catalyst.
3. preparation method according to claim 2, it is characterized in that: described silver salt, nickel salt, yttrium salt are silver nitrate, nickel nitrate, yttrium nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100740172A CN102626637B (en) | 2012-03-20 | 2012-03-20 | Catalyst for one-step preparation of epoxyethane from ethane, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100740172A CN102626637B (en) | 2012-03-20 | 2012-03-20 | Catalyst for one-step preparation of epoxyethane from ethane, and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102626637A CN102626637A (en) | 2012-08-08 |
| CN102626637B true CN102626637B (en) | 2013-11-06 |
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ID=46585137
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100740172A Expired - Fee Related CN102626637B (en) | 2012-03-20 | 2012-03-20 | Catalyst for one-step preparation of epoxyethane from ethane, and preparation method thereof |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5502020A (en) * | 1993-04-14 | 1996-03-26 | Mitsubishi Petrochemical Co., Ltd. | Catalyst for production of ethylene oxide and process for producing the catalyst |
| CN101265242B (en) * | 2008-04-16 | 2011-07-20 | 浙江师范大学 | Method for directly preparing epoxy ethane by ethane one-step oxidation |
| CN102091641B (en) * | 2010-12-03 | 2012-12-19 | 烟台万华聚氨酯股份有限公司 | Supported silver-cobalt or silver-nickel reductive ammonolysis catalyst as well as preparation method and applications thereof |
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2012
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